WO2018203537A1 - Impact absorption sheet and double-sided pressure-sensitive adhesive sheet - Google Patents
Impact absorption sheet and double-sided pressure-sensitive adhesive sheet Download PDFInfo
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- WO2018203537A1 WO2018203537A1 PCT/JP2018/017272 JP2018017272W WO2018203537A1 WO 2018203537 A1 WO2018203537 A1 WO 2018203537A1 JP 2018017272 W JP2018017272 W JP 2018017272W WO 2018203537 A1 WO2018203537 A1 WO 2018203537A1
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- sensitive adhesive
- impact
- sheet
- weight
- double
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Definitions
- the present invention relates to an impact absorbing sheet. Moreover, this invention relates to the double-sided adhesive sheet which has this impact-absorbing sheet.
- an adhesive tape is used for assembly.
- a front panel (cover panel) for protecting the surface of a portable electronic device is bonded to a touch panel module or a display panel module, or an adhesive is used to bond a touch panel module and a display panel module.
- Tape is used.
- Such an adhesive tape is used by being punched into a frame shape or the like and arranged around the display screen (for example, Patent Documents 1 and 2).
- Adhesive tapes used in portable electronic devices are required to have various performances including high adhesive strength. For example, even if an impact is applied, the tape does not peel off, and the component has a strong impact. There is also a need for impact resistance that does not add.
- a method for improving the impact resistance of the pressure-sensitive adhesive tape for example, a method using a buffering base material such as a foamed material can be mentioned.
- Patent Document 3 describes a pressure-sensitive adhesive sheet for electronic equipment comprising a cross-linked polyolefin resin foam sheet and a specific acrylic pressure-sensitive adhesive layer laminated and integrated on one surface of the cross-linked polyolefin resin foam sheet.
- An object of the present invention is to provide an impact absorbing sheet having high impact resistance and excellent resistance to sebum. Moreover, an object of this invention is to provide the double-sided adhesive sheet which has this impact-absorbing sheet.
- the present invention is an impact-absorbing sheet having an impact-absorbing layer, wherein the impact-absorbing layer has a maximum loss tangent tan ⁇ at a frequency of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6.5 Hz at 23 ° C. Is an impact-absorbing sheet having a crystallinity of 2% or more. The present invention is described in detail below.
- the oil accumulates in the bubble portion of the foam by being exposed to sebum, and the fat oozes out into the pressure-sensitive adhesive layer. I found that it would lead to peeling. Therefore, it was considered to use a non-foamed material instead of the foam as the base material, but the non-foamed material was dissolved or swollen by contact with sebum, and the shape collapsed, and the adhesive tape could be peeled off.
- the shock absorbing sheet having a shock absorbing layer which is preferably used as the base material of the double-sided pressure-sensitive adhesive sheet, the present inventors set the maximum value of the loss tangent tan ⁇ at a specific frequency at 23 ° C.
- the present invention has been completed.
- an impact absorbing layer even when an impact such as dropping is applied, the energy due to the impact is effectively dissipated as heat or due to deformation, and peeling of the double-sided pressure-sensitive adhesive sheet is suppressed.
- the denseness of the shock absorbing layer is high, so that the penetration and absorption of fat are suppressed, and peeling of the double-sided pressure-sensitive adhesive sheet is suppressed.
- the shock absorbing sheet of the present invention has a shock absorbing layer.
- the shock absorbing layer has a maximum loss tangent tan ⁇ of 0.7 or more at a frequency of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6.5 Hz at 23 ° C. and a crystallinity of 2% or more. is there.
- the maximum value of the loss tangent tan ⁇ is 0.7 or more, the impact resistance of the shock absorbing layer is improved. For this reason, even when a shock such as a drop is applied when the shock-absorbing sheet of the present invention is used as a base material for a double-sided pressure-sensitive adhesive sheet, energy due to the shock is effectively dissipated as heat or due to deformation. Peeling of the pressure sensitive adhesive sheet is suppressed.
- the maximum value of the loss tangent tan ⁇ may be 0.7 or more, but is preferably 0.8 or more, and more preferably 0.9 or more.
- the upper limit of the maximum value of the loss tangent tan ⁇ is not particularly limited, but when the viscous component in the shock absorbing layer increases and the maximum value of the loss tangent tan ⁇ becomes too large, the shock absorbing layer absorbs the shock.
- a preferred upper limit is 3.0, and a more preferred upper limit is 2.7, because plastic deformation is likely.
- the maximum value of the loss tangent tan ⁇ at a frequency of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6.5 Hz at 23 ° C. is a dynamic viscoelasticity measuring device (for example, Rheogel-E4000 manufactured by UBM). It can be judged by measuring the elastic modulus of the shock absorbing layer using, and synthesizing a master curve. At this time, the “maximum value” of the loss tangent tan ⁇ does not necessarily have to exist within the frequency range of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6.5 Hz.
- the “maximum value” exists in the frequency range of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6.5 Hz, an impact was applied to the shock absorbing layer at a temperature higher or lower than 23 ° C. Even in this case, the shock absorbing layer can easily absorb the shock stably.
- the frequency of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6.5 Hz means that an object can be freely dropped from a height of several tens of centimeters to one tens of centimeters with respect to the shock absorbing layer. Then, the frequency assumes a frequency when the shock absorbing layer is displaced from several micrometers to several tens of micrometers. That is, the frequency is assumed when an impact such as dropping is applied to the portable electronic device.
- the crystallinity When the crystallinity is 2% or more, resistance of the shock absorbing layer to sebum is improved. For this reason, even when it is exposed to sebum when the shock absorbing sheet of the present invention is used as a base material for a double-sided pressure-sensitive adhesive sheet, the penetration and absorption of fats are suppressed due to the high density of the shock absorbing layer. Thus, peeling of the double-sided pressure-sensitive adhesive sheet is suppressed.
- the crystallinity may be 2% or more, preferably 4% or more, and more preferably 6% or more.
- the upper limit of the crystallinity is not particularly limited, but if the crystallinity is too high, the shock absorbing layer is less likely to be plastically deformed when absorbing the impact, so the preferred upper limit is 15%, and the more preferred upper limit is 10%.
- the crystallinity can be measured using an X-ray diffractometer (for example, SmartLab manufactured by Rigaku Corporation). Specifically, the shock absorbing layer is irradiated with X-rays, and in the obtained diffraction information (diffraction profile), the scattering region derived from the amorphous portion and the scattering region derived from the crystal portion are separated, and the total scattering integration is performed. Calculated as the ratio of the integrated intensity of crystal scattering to the intensity. Waveform separation between the amorphous portion and the crystal portion can be performed by analysis software using a multiple peak separation program.
- the composition of the shock absorbing layer may be adjusted within the range described later.
- the shock absorbing layer preferably contains an olefin elastomer having a crystal structure.
- the crystal structure in the olefin-based elastomer having the above crystal structure means a structure that exhibits crystallinity due to, for example, a linear connection of monomers in a polymer (polymer compound).
- Examples of the compound having such a structure include linear polyolefin.
- the olefin elastomer having the above crystal structure may be a random copolymer or a block copolymer.
- examples of the random copolymer include linear low density polyethylene (LLDPE) and high density polyethylene (HDPE).
- examples of the block copolymer include olefin crystal-ethylene-butylene-olefin crystal (CEBC) block polymer, styrene-ethylene-butylene-olefin crystal (SEBC) block polymer, and the like.
- CEBC olefin crystal-ethylene-butylene-olefin crystal
- SEBC styrene-ethylene-butylene-olefin crystal
- the CEBC block polymer is preferred because the crystal structure becomes denser due to the continuous linear portion.
- the olefin-based elastomer having the crystal structure is preferably a non-crosslinked type because it is difficult to exhibit flexibility when it is a crosslinked type.
- the olefin elastomer having the crystal structure may be used in combination with other elastomers.
- the difference in solubility parameter (SP value) between the olefin elastomer having the crystal structure and the other elastomer is preferably 2 or less.
- the compatibility between the olefin elastomer having the crystal structure and the other elastomer is increased, and the shock absorbing sheet of the present invention is used as a base material for a double-sided pressure-sensitive adhesive sheet.
- the difference in SP value is more preferably 1 or less.
- the solubility parameter (SP value) (unit: (cal / cm 3 ) 1/2 ) is an index representing the affinity between the resin or the elastomer, and can be calculated by, for example, the Fedors equation shown below. .
- the ratio of the olefin elastomer having the crystal structure to the total of the olefin elastomer having the crystal structure and the other elastomer ( The weight ratio is preferably 60% by weight or more. If the ratio is 60% by weight or more, it becomes easy to adjust the maximum value of the loss tangent tan ⁇ within the above range and the crystallinity within the above range, and the impact resistance of the shock absorbing layer. And resistance to sebum. The ratio is more preferably 70% by weight or more.
- the other elastomers are not particularly limited, and examples thereof include styrene elastomers, acrylic elastomers, urethane elastomers, ester elastomers, vinyl chloride elastomers, and amide elastomers. These elastomers may be used alone or in combination of two or more. Among these, from the viewpoints of adjusting the maximum value of the loss tangent tan ⁇ within the above range and adjusting the crystallinity within the above range, a styrene-based elastomer is preferable.
- the styrene-based elastomer is not particularly limited as long as it has rubber elasticity at room temperature.
- a styrene-based elastomer having a diblock or triblock structure of a polystyrene layer called a hard segment and a soft segment such as ethylene-butylene, ethylene-propylene, or ethylene-butadiene is more preferable.
- styrenic elastomer examples include styrene-butadiene-styrene (SBS) block copolymer, styrene-butadiene-butylene-styrene (SBBS) block copolymer, styrene-ethylene-butylene-styrene (SEBS) block copolymer, water Examples thereof include styrene-butylene rubber (HSBR), styrene-ethylene-propylene-styrene (SEPS) block copolymer, styrene-isobutylene-styrene (SIBS) block copolymer, and styrene-isoprene-styrene (SIS) block copolymer.
- SEBS and SEPS are more preferable because they do not have a double bond in the molecular structure and are relatively stable to heat and light.
- the styrene content of the styrenic elastomer is not particularly limited, but a preferred lower limit is 3% by weight and a preferred upper limit is 30% by weight.
- a preferred lower limit is 3% by weight or more
- the heat resistance or cohesion of the shock absorbing layer is improved.
- the styrene content is 30% by weight or less, the flexibility of the styrene-based elastomer is increased, the maximum value of the loss tangent tan ⁇ is increased, and the impact resistance of the shock absorbing layer is improved.
- a more preferable lower limit of the styrene content is 4% by weight, and a more preferable upper limit is 25% by weight, a still more preferable lower limit is 5% by weight, and a still more preferable upper limit is 20% by weight.
- the content of each block such as styrene in the styrene elastomer can be measured by 1 H-NMR (1H-nuclear magnetic resonance) measurement or 13 C-NMR.
- the content of the ethylene skeleton in the soft segment of the styrene-based elastomer is not particularly limited, but a preferable upper limit in 100% by weight of the entire soft segment is 60% by weight.
- a preferable upper limit in 100% by weight of the entire soft segment is 60% by weight.
- the flexibility of the styrenic elastomer is increased, the maximum value of the loss tangent tan ⁇ is increased, and the impact resistance of the shock absorbing layer is improved.
- a more preferable upper limit of the content of the ethylene skeleton is 50% by weight, and a more preferable upper limit is 40% by weight.
- the content of the ethylene skeleton in the soft segment is preferably in the above range.
- the content of the ethylene skeleton in the soft segment is preferably 3% by weight or more, more preferably 4% by weight or more, and more preferably 5% by weight or more. More preferably.
- the shock absorbing layer has an appropriate glass transition temperature, so the maximum value of the loss tangent tan ⁇ is Easy to adjust to the range.
- the content of the butylene skeleton in the soft segment when the styrene-based elastomer is SEBS is not particularly limited, but is preferably 45% by weight or more. By setting the content of the butylene skeleton to 45% by weight or more, excellent impact resistance can be exhibited.
- the content of the butylene skeleton is more preferably 60% by weight or more, and further preferably 70% by weight or more.
- the total content of ethylene and 1,4-butadiene in the SBBS soft segment is preferably 60% by weight or less, more preferably 50% by weight or less, and further preferably 40% by weight or less. preferable.
- tan ⁇ can be controlled to be high, but since the frequency of the peak value of tan ⁇ may be outside the specified range, the ethylene skeleton is included in the soft segment. More preferably, the tan ⁇ peak position is adjusted.
- the impact absorbing layer may contain a tackifier resin.
- a tackifying resin By blending a tackifying resin into the impact absorbing layer, the maximum value of the loss tangent tan ⁇ can be easily adjusted to the above range.
- the tackifying resin is not particularly limited, and examples thereof include a terpene resin, a rosin resin, and a petroleum resin.
- the impact absorbing layer may contain a softening agent.
- a softening agent flexibility is improved and impact resistance is improved.
- the impact absorbing layer contains a softening agent, the adhesion between the double-sided pressure-sensitive adhesive sheet of the present invention and the adherend is improved when the shock-absorbing sheet of the present invention is used as a base material of the double-sided pressure-sensitive adhesive sheet.
- the softener is not particularly limited, and examples thereof include petroleum softeners (paraffinic oil), liquid rubber softeners, dibasic acid esters, plant softeners, oil softeners, and the like.
- the softening agent preferably has a small difference in solubility parameter (SP value) with the resin constituting the shock absorbing layer.
- the SP value of the softening agent is preferably 9 or less. By using such a softening agent, it is possible to improve flexibility while suppressing delamination caused by bleeding of the softening agent on the surface of the shock absorbing layer.
- the petroleum softener paraffinic oil
- examples of the petroleum softener (paraffinic oil) include Fukkorflex 2050N (Fuji Kosan Co., Ltd.), Diana Process Oil PW90 (Idemitsu Kosan Co., Ltd.), and the like.
- An example of the liquid rubber softener is polybutene. The polybutene preferably has a number average molecular weight of 1000 or more.
- the content of the softening agent is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the resin constituting the shock absorbing layer is 50 parts by weight, and a preferable upper limit is 250 parts by weight. If content of the said softening agent is 50 weight part or more, the softness
- the minimum with more preferable content of the said softener is 100 weight part, and a more preferable upper limit is 200 weight part.
- the impact absorbing layer may contain an antioxidant or an ultraviolet absorber because weather resistance is improved.
- the antioxidant or ultraviolet absorber is not particularly limited, and examples thereof include phenol-based, amine-based, and benzimidazole-based antioxidants and ultraviolet absorbers.
- examples of the phenolic antioxidant include NOCRACK NS-6 (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.).
- examples of the ultraviolet absorber include SEESORB 101 (manufactured by Cypro Corporation).
- the shock absorbing layer is preferably colored. By coloring the shock absorbing layer, the light of the liquid crystal display panel incorporated in the portable electronic device can be shielded by the shock absorbing layer.
- the colorant is not particularly limited, and pigments, dyes, and the like that are generally blended in pressure-sensitive adhesive sheets used for bonding and fixing components constituting a portable electronic device to the device main body can be used. Examples of the colorant include carbon black such as furnace black, thermal black, acetylene black, channel black, lamp black, and ketjen black.
- oxides such as iron oxide, titanium oxide, zinc oxide, magnesium oxide, cobalt oxide, copper oxide, chromium oxide, and alumina
- sulfates such as calcium sulfate, barium sulfate, iron sulfate, and mercury sulfate
- calcium carbonate, magnesium carbonate And carbonates such as dolomite.
- metal powders such as iron powder, copper powder, tin powder, lead powder and aluminum powder; organic pigments such as azo pigments, phthalocyanine pigments and dioxazine pigments; graphite and the like. Of these, carbon black is preferable.
- the content of the colorant in the shock absorbing layer is not particularly limited, but a preferred lower limit is 0.1% by weight, a preferred upper limit is 10% by weight, a more preferred lower limit is 0.3% by weight, and a more preferred upper limit is 5%. % By weight. If too much of the colorant is added, uneven coloring may occur in the impact absorbing layer due to poor dispersion of the colorant.
- the preferable lower limit of the OD value of the shock absorbing layer is 2, and the preferable upper limit is 7.
- the OD value is 2 or more, the shock absorbing layer can sufficiently suppress light transmission both in the width direction and in the thickness direction.
- the OD value is 7 or less, the flexibility of the shock absorbing layer is not impaired and the impact resistance can be maintained.
- the more preferable lower limit of the OD value is 4, and the more preferable upper limit is 6.
- the OD value can be measured with a haze meter (for example, NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.).
- the impact absorbing layer may contain fine particles for the purpose of imparting heat resistance, rigidity, conductivity, etc., or weight reduction.
- the fine particles are not particularly limited.
- the shock absorbing layer may have a foam structure for the purpose of imparting flexibility. Examples of the method for forming the foam structure include chemical foaming with a foaming agent, physical foaming by gas kneading, and the like, and mixing hollow fine particles.
- the thickness of the said shock absorption layer is not specifically limited, A preferable minimum is 50 micrometers and a preferable upper limit is 400 micrometers. If the said thickness is 50 micrometers or more, the intensity
- the shock absorbing sheet of the present invention preferably further has an outer layer laminated and integrated on at least one surface of the shock absorbing layer.
- the outer layer may be formed only on one side of the shock absorbing layer or may be formed on both sides.
- the outer layer preferably has a tensile modulus of 200 MPa or more. If the said tensile elasticity modulus is 200 Mpa or more, the tolerance to sebum of an impact-absorbing sheet, punching workability, and handleability will improve more.
- the upper limit of the tensile elastic modulus is not particularly limited, but if it is too high, the flexibility of the outer layer is lowered, and the impact resistance of the laminate with the shock absorbing layer may be lowered. Therefore, the preferred upper limit is 2000 MPa, more A preferable upper limit is 1800 MPa.
- the tensile modulus can be measured according to the ASTM D638 method.
- the outer layer preferably has a difference in solubility parameter (SP value) of 2 or less from the shock absorbing layer.
- SP value solubility parameter
- the difference in SP value is more preferably 1 or less.
- the resin which comprises the said outer layer is not specifically limited, For example, polyolefin, a thermoplastic elastomer, etc. are mentioned. Especially, by using polyolefin, the anchor property of the said shock absorption layer and the said outer layer becomes favorable, and can suppress the dispersion
- the polyolefin include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and polypropylene (PP).
- the thermoplastic elastomer include polyamide (PA) and polybutylene terephthalate (PBT).
- the impact absorbing sheet of the present invention may further have other layers.
- electroconductivity can be provided to an impact-absorbing sheet by laminating a conductive film on the impact-absorbing layer.
- a primer to the shock absorbing layer, adhesion between the shock absorbing layer and a pressure-sensitive adhesive layer to be described later can be improved, or various performances can be imparted to the shock absorbing layer.
- the impact absorbing sheet of the present invention preferably has a tensile elastic modulus of 150 MPa or more. If the said tensile elasticity modulus is 150 Mpa or more, the tolerance to sebum of an impact-absorbing sheet, punching workability, and handleability will improve more.
- a more preferable lower limit of the tensile elastic modulus is 300 MPa, and a more preferable lower limit is 500 MPa.
- the thickness of the impact-absorbing sheet of the present invention is not particularly limited, but a preferable lower limit is 60 ⁇ m and a preferable upper limit is 1000 ⁇ m. If the said thickness is 60 micrometers or more, the intensity
- the manufacturing method of the impact-absorbing sheet of this invention is not specifically limited, For example, the method of supplying the material which comprises the said impact-absorbing layer to a melt extruder, and extruding in a sheet form etc. are mentioned. Moreover, when the impact-absorbing sheet of this invention has another layer in addition to the said impact-absorbing layer, the method etc. which coextrude the material of each layer and obtain a multilayer structure sheet etc. are mentioned, for example.
- the use of the shock absorbing sheet of the present invention is not particularly limited, but it can be used as a base material for a pressure sensitive adhesive sheet for bonding and fixing components constituting a portable electronic device to the main body of a device or a pressure sensitive adhesive sheet for bonding and fixing a vehicle-mounted component Is preferred.
- the portable electronic device is not limited to a conventional rigid portable electronic device, and may be a portable electronic device that is exposed to more severe conditions such as a wearable terminal and a bendable (bending) terminal.
- the shape of the impact-absorbing sheet of the present invention in these uses is not particularly limited, and examples thereof include a rectangle, a frame shape, a circle, an ellipse, and a donut shape.
- a double-sided pressure-sensitive adhesive sheet having the shock-absorbing sheet of the present invention and a pressure-sensitive adhesive layer laminated and integrated on both surfaces of the shock-absorbing sheet of the present invention is also one aspect of the present invention.
- the pressure-sensitive adhesive layers on both sides may have the same composition or different compositions.
- the impact absorbing layer preferably has a 25% compressive strength of 930 kPa or less.
- the 25% compressive strength is 930 kPa or less, the adhesion between the double-sided PSA sheet and the adherend is improved. More specifically, when sticking a double-sided adhesive sheet to a to-be-adhered body, it can suppress that the air between an to-be-adhered body and a double-sided adhesive sheet becomes difficult to escape
- a more preferable upper limit of the 25% compressive strength of the shock absorbing layer is 800 kPa, and a more preferable upper limit is 600 kPa.
- the composition of the shock absorbing layer may be adjusted.
- the said shock absorption layer contains the said softener.
- the 25% compressive strength of the shock absorbing layer can be measured as follows. First, the impact absorbing layer to be measured is cut into a size of 20 mm ⁇ 20 mm and then laminated so as to have a thickness of 6 mm to produce a test piece. Next, the test piece is compressed by a thickness of 25% at a speed of 10 mm / min using a universal testing machine (for example, Autograph AGS-X manufactured by Shimadzu Corporation), and the pressure required for the compression is measured.
- a universal testing machine for example, Autograph AGS-X manufactured by Shimadzu Corporation
- the acrylic pressure-sensitive adhesive is not particularly limited, but contains a (meth) acrylate copolymer having a structural unit derived from fluorine-containing (meth) acrylate (hereinafter also referred to as “fluorine-containing (meth) acrylate copolymer”). It is preferable.
- (meth) acrylate means acrylate or methacrylate.
- the structural unit derived from the above fluorine-containing (meth) acrylate is such that fluorine itself exhibits high water and oil repellency, and sebum is less likely to enter the molecular chain due to dense packing of fluorine atoms. High resistance to sebum can be imparted to the pressure-sensitive adhesive layer.
- the said acrylic adhesive contains a fluorine-containing (meth) acrylate copolymer, the tack property of the said adhesive layer can be maintained.
- fluorine-containing (meth) acrylate examples include 2,2,2-trifluoroethyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (Perfluorobutyl) ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 1H , 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H-1- (trifluoromethyl) trifluoroethyl acrylate IH, IH, 3H-hexafluor
- a preferable lower limit is 30% by weight, and a preferable upper limit is 80% by weight. If the said content is 30 weight% or more, the tolerance to the sebum of the said adhesive layer will improve. If the said content is 80 weight% or less, the said acrylic adhesive will not become hard too much and adhesive force will improve.
- the more preferable lower limit of the content is 40% by weight, and the more preferable upper limit is 60% by weight.
- the fluorine-containing (meth) acrylate copolymer preferably further contains a structural unit derived from (meth) acrylate having an alkyl group having 2 or less carbon atoms.
- the tolerance to sebum can further be improved.
- Examples of the (meth) acrylate having an alkyl group having 2 or less carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate. Among them, ethyl acrylate is preferable because the acrylic pressure-sensitive adhesive does not become too hard and the adhesive strength is improved.
- the content of the structural unit derived from the (meth) acrylate having an alkyl group having 2 or less carbon atoms in the fluorine-containing (meth) acrylate copolymer is not particularly limited, but a preferred lower limit is 15% by weight and a preferred upper limit is 40% by weight. When the content is within the above range, the pressure-sensitive adhesive layer can be more resistant to sebum. A more preferable lower limit of the content is 20% by weight, and a more preferable upper limit is 30% by weight.
- the fluorine-containing (meth) acrylate copolymer preferably further contains a structural unit derived from a monomer having a crosslinkable functional group.
- the fluorine-containing (meth) acrylate copolymer contains a structural unit derived from the monomer having the crosslinkable functional group
- the fluorine-containing (meth) acrylate copolymer chain is crosslinked when a crosslinking agent is used in combination. .
- the gel fraction and the swelling ratio can be adjusted by adjusting the degree of crosslinking.
- Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, and a nitrile group. Especially, since adjustment of the gel fraction of the said adhesive layer is easy, a hydroxyl group or a carboxyl group is preferable.
- Examples of the monomer having a hydroxyl group include (meth) acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
- (meth) acrylic acid is mentioned, for example.
- Examples of the monomer having a glycidyl group include glycidyl (meth) acrylate.
- Examples of the monomer having an amide group include hydroxyethyl acrylamide, isopropyl acrylamide, dimethylaminopropyl acrylamide and the like.
- Examples of the monomer having a nitrile group include acrylonitrile. These monomers having a crosslinkable functional group may be used alone or in combination.
- content of the structural unit derived from the monomer which has the said crosslinkable functional group in the said fluorine-containing (meth) acrylate copolymer is not specifically limited, A preferable minimum is 1 weight% and a preferable upper limit is 5 weight%. When the content is in the above range, the swelling rate and gel fraction can be easily adjusted, and the resistance of the pressure-sensitive adhesive layer to sebum is improved.
- the said fluorine-containing (meth) acrylate copolymer may further contain the structural unit derived from another monomer in the range which does not inhibit the effect of this invention.
- the other monomer include propyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, isobornyl acrylate, benzyl acrylate, phenoxyethyl acrylate, and vinyl acetate.
- the fluorine-containing (meth) acrylate copolymer preferably has a lower limit of 500,000 and an upper limit of 2,000,000 for the weight average molecular weight (Mw).
- Mw weight average molecular weight
- the weight average molecular weight (Mw) can be adjusted by polymerization conditions (for example, the type or amount of polymerization initiator, polymerization temperature, monomer concentration, etc.).
- the weight average molecular weight (Mw) is a weight average molecular weight in terms of standard polystyrene by GPC (Gel Permeation Chromatography).
- an acrylic monomer derived from the structural unit may be radically reacted in the presence of a polymerization initiator.
- the polymerization method is not particularly limited, and a conventionally known method can be used. Examples include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like. Among these, solution polymerization is preferable because synthesis is simple.
- reaction solvent examples include ethyl acetate, toluene, methyl ethyl ketone, methyl sulfoxide, ethanol, acetone, diethyl ether and the like. These reaction solvents may be used alone or in combination of two or more.
- the said polymerization initiator is not specifically limited, For example, an organic peroxide, an azo compound, etc. are mentioned.
- the organic peroxide include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5 -Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Examples include isobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxylaurate.
- the azo compound include azobisisobutyronitrile and azobiscyclohexanecarbonitrile.
- the acrylic pressure-sensitive adhesive preferably contains a crosslinking agent.
- a crosslinked structure can be constructed
- the said crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned. Of these, isocyanate crosslinking agents and epoxy crosslinking agents are preferred.
- the amount of the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the fluorine-containing (meth) acrylate copolymer.
- the acrylic pressure-sensitive adhesive may contain a silane coupling agent.
- the acrylic pressure-sensitive adhesive contains a silane coupling agent, the adhesiveness of the pressure-sensitive adhesive layer to the adherend is improved, so that the resistance to sebum is improved.
- the silane coupling agent is not particularly limited.
- content of the said silane coupling agent is not specifically limited,
- the preferable minimum with respect to 100 weight part of said acrylic adhesives is 0.1 weight part, and a preferable upper limit is 5 weight part.
- a preferable upper limit is 5 weight part.
- the content is 0.1 part by weight or more, resistance to sebum can be further increased.
- the said content being 5 weight part or less, the adhesive residue at the time of re-peeling can be suppressed.
- a more preferable lower limit of the content is 1 part by weight, and a more preferable upper limit is 3 parts by weight.
- the pressure-sensitive adhesive layer contains additives such as plasticizers, emulsifiers, softeners, fillers, pigments and dyes, tackifiers such as rosin resins and terpene resins, and other resins as necessary. It may be.
- the pressure-sensitive adhesive layer preferably has a gel fraction of 5% by weight or more. It becomes easy to adjust the swelling rate of the said adhesive layer because the said gel fraction is 5 weight% or more, and the tolerance to sebum improves. A more preferable lower limit of the gel fraction is 10% by weight. Although the upper limit of the said gel fraction is not specifically limited, A preferable upper limit is 95% weight and a more preferable upper limit is 90% weight.
- the thickness of the said adhesive layer is not specifically limited, A preferable minimum is 5 micrometers and a preferable upper limit is 50 micrometers.
- a preferable minimum is 5 micrometers and a preferable upper limit is 50 micrometers.
- the thickness of the pressure-sensitive adhesive layer is 5 ⁇ m or more, the double-sided pressure-sensitive adhesive sheet can be made more excellent in adhesiveness.
- the thickness of the pressure-sensitive adhesive layer is 50 ⁇ m or less, the double-sided pressure-sensitive adhesive sheet can be made more excellent in processability.
- the double-sided pressure-sensitive adhesive sheet of the present invention preferably has a total thickness of 100 to 400 ⁇ m. If the said total thickness is 100 micrometers or more, the impact resistance of a double-sided adhesive sheet will improve. If the said total thickness is 400 micrometers or less, a double-sided adhesive sheet will become a thing suitable for the use which adheres and fixes the component which comprises a portable electronic device to an apparatus main body.
- the compressive strength of the double-sided pressure-sensitive adhesive sheet of the present invention is not particularly limited, but the preferred lower limit of 25% compressive strength is 10 kPa, and the preferred upper limit is 2000 kPa.
- the 25% compressive strength is 10 kPa or more
- the double-sided pressure-sensitive adhesive sheet is pressure-bonded to the adherend, it is possible to suppress the impact absorbing sheet that is the base material from seeping out sideways.
- the 25% compressive strength is 2000 kPa or less, when the double-sided pressure-sensitive adhesive sheet is attached to the adherend, the air between the adherend and the double-sided pressure-sensitive adhesive sheet is difficult to escape and the sticking property is reduced. Can be suppressed.
- the more preferable lower limit of the 25% compressive strength is 30 kPa
- the more preferable upper limit is 1000 kPa.
- a solution of an acrylic pressure-sensitive adhesive a is prepared by adding a solvent to a fluorine-containing (meth) acrylate copolymer and, if necessary, a crosslinking agent, etc., and the solution of the acrylic pressure-sensitive adhesive a is a base material for an impact absorbing sheet
- the adhesive layer a is formed by completely drying and removing the solvent in the solution.
- the release film is superimposed on the formed pressure-sensitive adhesive layer a so that the release treatment surface faces the pressure-sensitive adhesive layer a.
- a laminated film having the pressure-sensitive adhesive layer b formed on the surface of the release film is produced.
- the pressure-sensitive adhesive layer b of the obtained laminated film is overlapped with the back surface of the shock absorbing sheet (the surface on which the pressure-sensitive adhesive layer a is not formed) to produce a laminate.
- a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both sides of the impact-absorbing sheet and having the surface of the pressure-sensitive adhesive layer covered with a release film can be obtained. .
- two sets of laminated films are produced in the same manner, and these laminated films are superposed on both sides of the shock absorbing sheet as a base material with the adhesive layer of the laminated film facing the shock absorbing sheet.
- a laminated body may be prepared, and the laminated body may be pressed by a rubber roller or the like. Thereby, the double-sided adhesive sheet which has an adhesive layer on both surfaces of an impact-absorbing sheet, and the surface of the adhesive layer was covered with the release film can be obtained.
- the double-sided pressure-sensitive adhesive sheet of the present invention is not particularly limited, the use for bonding and fixing components constituting the portable electronic device to the device main body and the use for bonding and fixing vehicle-mounted components are preferable.
- the double-sided pressure-sensitive adhesive sheet of the present invention can be used, for example, as a double-sided pressure-sensitive adhesive sheet that adheres and fixes a liquid crystal display panel of a portable electronic device to the device body.
- the portable electronic device is not limited to a conventional rigid portable electronic device, and may be a portable electronic device that is exposed to more severe conditions such as a wearable terminal and a bendable (bending) terminal.
- the shape of the double-sided pressure-sensitive adhesive sheet of the present invention in these applications is not particularly limited, and examples thereof include a rectangle, a frame shape, a circle, an ellipse, and a donut shape.
- the double-sided pressure-sensitive adhesive sheet of the present invention has a frame-like shape, such as a front panel fixing pressure-sensitive adhesive sheet, a back panel fixing pressure-sensitive adhesive sheet, and a backlight unit fixing pressure-sensitive adhesive sheet in portable electronic devices. Even when added, the portable electronic device can be effectively prevented from being damaged. In particular, high impact resistance can be exhibited even when the frame-like pressure-sensitive adhesive sheet is narrowed (for example, a width of 1.0 mm or less) with the recent increase in screen size of portable electronic devices.
- the present invention it is possible to provide an impact-absorbing sheet having high impact resistance and excellent resistance to sebum. Moreover, according to this invention, the double-sided adhesive sheet which has this impact-absorbing sheet can be provided.
- Example 1 (1) Production of Shock Absorbing Sheet
- materials constituting the shock absorbing layer 100 parts by weight of olefin crystal-ethylene-butylene-olefin crystal (CEBC) block polymer (Dynalon 6200 manufactured by JSR), 3 parts by weight of carbon black, was used.
- a material constituting the outer layer low density polyethylene (LDPE) (PE in Table 1) was used.
- the material constituting the shock absorbing layer and the material constituting the outer layer were melted at 200 ° C., and these molten resins were laminated in a multilayer die while being extruded (coextrusion temperature 200 ° C.). Thereafter, by cooling, an impact absorbing sheet was obtained in which an outer layer having a thickness of 10 ⁇ m was laminated on both sides of a non-foamed impact absorbing layer having a thickness of 60 ⁇ m.
- the shock absorbing layer was cut into a width of 5 mm ⁇ 30 mm, and the long side of 30 mm was chucked with a dynamic viscoelasticity measuring apparatus (Rheogel-E4000 manufactured by UBM) with a chuck interval of 15 mm.
- a dynamic viscoelasticity measuring apparatus Heogel-E4000 manufactured by UBM
- a frequency at 23 ° C. 1.0 ⁇ 10 3
- the maximum value of the loss tangent tan ⁇ at 1.0 ⁇ 10 6.5 Hz was calculated.
- the frequency at which the loss tangent tan ⁇ takes the maximum value was confirmed.
- the shock absorbing layer was cut into 30 mm ⁇ 30 mm, and the shock absorbing layer was irradiated with X-rays using an X-ray diffractometer (SmartLab manufactured by Rigaku Corporation).
- X-ray diffractometer SmartLab manufactured by Rigaku Corporation.
- the scattering region derived from the crystal portion and the scattering region derived from the crystal portion were separated, and the crystallinity was calculated as the ratio of the crystal scattering integrated intensity to the total scattering integrated intensity.
- the transmittance was measured with a haze meter (NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.), and the OD value of the shock absorbing layer was calculated.
- the SP values of the shock absorbing layer and the outer layer were calculated based on the structural units of the polymers constituting the shock absorbing layer and the outer layer and the Fedors equation.
- the tensile elastic modulus of the outer layer and the impact absorbing sheet was calculated based on the ASTM D638 method.
- a polymerization initiator solution obtained by diluting 0.1 parts by weight of azobisisobutyronitrile 10 times with ethyl acetate as a polymerization initiator was charged again into the reaction vessel, and a polymerization reaction was performed for 4 hours.
- An acrylate copolymer-containing solution was obtained.
- 1 part by weight of Tetrad C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a cross-linking agent is added to 100 parts by weight of the (meth) acrylate copolymer to obtain an adhesive A. It was.
- Adhesive A was applied to a 75 ⁇ m-thick release PET film that had been subjected to silicon release treatment using an applicator and dried at 110 ° C. for 3 minutes to form a 35 ⁇ m-thick pressure-sensitive adhesive layer did.
- This pressure-sensitive adhesive layer was bonded to the impact-absorbing sheet obtained above using a silicon roller to obtain a single-sided pressure-sensitive adhesive sheet.
- the shock absorbing sheet was previously subjected to corona treatment on both sides under the conditions of 270 W and 18 m / min using a corona treatment device (“CT-0212” manufactured by Kasuga Denki Co., Ltd.).
- the release PET film on the surface opposite to the impact-absorbing sheet was peeled off, and the same pressure-sensitive adhesive layer as above was bonded. Thereafter, curing was performed at 40 ° C. for 48 hours. This obtained the double-sided adhesive sheet which both surfaces were covered with the mold release PET film.
- SEPS styrene-ethylene-propylene-styrene
- Example 3 A double-sided PSA sheet was obtained in the same manner as in Example 2 except that the CEBC: SEPS ratio was 6: 4.
- Example 4 A double-sided PSA sheet was obtained in the same manner as in Example 2 except that the CEBC: SEPS ratio was 4: 6.
- Example 5 A double-sided PSA sheet was obtained in the same manner as in Example 1 except that polypropylene (PP) was used for the outer layer.
- PP polypropylene
- Example 6 A double-sided PSA sheet was obtained in the same manner as in Example 1 except that the blending amount of carbon black was 1 part by weight with respect to 100 parts by weight of the block polymer and the OD value was adjusted to 2.5.
- Example 7 A double-sided PSA sheet was obtained in the same manner as in Example 1 except that the blending amount of carbon black was 6 parts by weight with respect to 100 parts by weight of the block polymer and the OD value was adjusted to 6.6.
- Example 8 In the preparation of the pressure-sensitive adhesive, the monomer added dropwise was changed to 23.5 parts by weight of butyl acrylate, 23.5 parts by weight of ethyl acrylate, 50 parts by weight of 2,2,2-trifluoroethyl acrylate, and 3 parts by weight of acrylic acid.
- a double-sided PSA sheet was obtained in the same manner as Example 1 except that the PSA B was obtained.
- Example 9 A double-sided PSA sheet was obtained in the same manner as in Example 2 except that PSA B was used instead of PSA A.
- Example 10 A double-sided PSA sheet was obtained in the same manner as in Example 1 except that a single layer was melt-extruded using only the material constituting the shock absorbing layer and no outer layer was formed.
- Example 11 A double-sided PSA sheet was obtained in the same manner as in Example 1 except that a softening agent (polybutene, number average molecular weight 1350) was added to the shock absorbing layer (70 parts by weight with respect to 30 parts by weight of CEBC).
- a softening agent polybutene, number average molecular weight 1350
- Example 12 A double-sided PSA sheet was obtained in the same manner as in Example 11 except that the amount of the softening agent was changed (50 parts by weight with respect to 50 parts by weight of CEBC).
- Example 13 A double-sided PSA sheet was obtained in the same manner as in Example 12 except that the softener was changed to a petroleum softener (paraffinic oil) (Diana Process Oil PW90, manufactured by Idemitsu Kosan Co., Ltd.).
- a petroleum softener paraffinic oil
- SEPS styrene-ethylene-propylene-styrene
- Example 2 A double-sided PSA sheet was obtained in the same manner as in Example 2 except that the CEBC: SEPS ratio was 2: 8.
- Example 3 A double-sided PSA sheet was obtained in the same manner as in Example 1 except that a PET (polyethylene terephthalate) film (E5100 manufactured by Toyobo Co., Ltd., thickness 75 ⁇ m) was used as the impact absorbing sheet.
- PET polyethylene terephthalate
- FIG. 1 the schematic diagram which shows the drop impact test of the double-sided adhesive sheet obtained by the Example and the comparative example is shown.
- the obtained double-sided PSA sheet was punched into an outer diameter of 46 mm, a length of 61 mm, an inner diameter of 44 mm, and a length of 59 mm to produce a frame-shaped test piece having a width of 1 mm.
- the test piece 41 is peeled off from the polycarbonate plate 43 having a thickness of 38 mm and a square hole having a width of 38 mm and a length of 50 mm in the center portion. Pasted to be located in.
- a polycarbonate plate 42 having a width of 55 mm, a length of 65 mm, and a thickness of 1 mm was pasted from the upper surface of the test piece 41 so that the test piece 41 was positioned substantially at the center, and the test apparatus was assembled. Thereafter, a pressure of 5 kgf was applied for 10 seconds from the side of the polycarbonate plate positioned on the upper surface of the test apparatus, and the polycarbonate plate positioned on the upper and lower sides and the test piece were pressed and left at room temperature for 24 hours.
- the oleic acid swelling rate of the shock absorbing layer is preferably 100 to 300% by weight, more preferably 100 to 200% by weight, it can exhibit high resistance to deterioration due to oleic acid, the main component of sebum. I can judge.
- Table 1 the determination when the oleic acid swelling ratio is 100% by weight or more is ⁇ , and the determination when the shock absorbing layer is dissolved by immersion (the oleic acid swelling ratio is less than 100% by weight) was marked with x.
- Adhesion evaluation (adhesion area evaluation)
- One surface of the double-sided PSA sheet obtained in the examples and comparative examples was attached to a glass plate having a thickness of 2 mm.
- the double-sided pressure-sensitive adhesive sheet and the glass plate were pasted so as to be in close contact with each other (the adhesion area was 100%).
- an acrylic plate having a thickness of 3 mm was prepared, and the other surface of the double-sided pressure-sensitive adhesive sheet was attached to the acrylic plate by reciprocating a 10 kg roller once.
- This test piece was photographed with a digital camera from the acrylic plate surface side (1920 ⁇ 1080 pixels, 4 times), and the obtained image was binarized in black and white (the threshold value was set to 1/2 of the maximum density).
- the area of the black part with respect to the area of the whole double-sided pressure-sensitive adhesive sheet was calculated as a bonding area ratio.
- the present invention it is possible to provide an impact-absorbing sheet having high impact resistance and excellent resistance to sebum. Moreover, according to this invention, the double-sided adhesive sheet which has this impact-absorbing sheet can be provided.
- Test piece (frame shape) 42 Polycarbonate plate (1mm thickness) 43 Polycarbonate plate (2mm thick) 44 Iron ball (300 g)
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Abstract
Description
粘着テープの耐衝撃性を向上させる方法として、例えば、発泡体等の緩衝性のある基材を用いる方法が挙げられる。特許文献3には、架橋ポリオレフィン系樹脂発泡シートと、上記架橋ポリオレフィン系樹脂発泡シートの一面に積層一体化された特定のアクリル系粘着剤層とを含む電子機器用粘着シートが記載されている。 Adhesive tapes used in portable electronic devices are required to have various performances including high adhesive strength. For example, even if an impact is applied, the tape does not peel off, and the component has a strong impact. There is also a need for impact resistance that does not add.
As a method for improving the impact resistance of the pressure-sensitive adhesive tape, for example, a method using a buffering base material such as a foamed material can be mentioned. Patent Document 3 describes a pressure-sensitive adhesive sheet for electronic equipment comprising a cross-linked polyolefin resin foam sheet and a specific acrylic pressure-sensitive adhesive layer laminated and integrated on one surface of the cross-linked polyolefin resin foam sheet.
また、携帯電子機器は、常に身に着けたり手元に置いたりして頻繁に使用され、また、タッチパネル等により素手で操作が行われる。このため、特許文献3に記載のような発泡体を基材とする粘着テープでは、皮脂によって粘着テープが劣化し、剥がれる不具合が生じやすくなっている。 In recent years, with the enlargement of screens of portable electronic devices, the size of adhesive tapes has been increasing. Further, since the adhesive tape is used in a shape such as a frame shape, the width of the adhesive tape is also being reduced. For this reason, the adhesive tape is required not to be peeled even in a small area, and the required level of impact resistance is increasing.
In addition, portable electronic devices are frequently used by being worn or placed at hand, and are operated with bare hands using a touch panel or the like. For this reason, in the adhesive tape which uses a foam as a base material as described in patent document 3, the adhesive tape deteriorates due to sebum, and a problem of peeling off easily occurs.
以下、本発明を詳述する。 The present invention is an impact-absorbing sheet having an impact-absorbing layer, wherein the impact-absorbing layer has a maximum loss tangent tan δ at a frequency of 1.0 × 10 3 to 1.0 × 10 6.5 Hz at 23 ° C. Is an impact-absorbing sheet having a crystallinity of 2% or more.
The present invention is described in detail below.
本発明者らは、両面粘着シートの基材として好適に用いられる、衝撃吸収層を有する衝撃吸収シートにおいて、衝撃吸収層の23℃における特定の周波数での損失正接tanδの最大値を特定値以上に調整し、かつ、結晶化度を特定値以上に調整することにより、耐衝撃性と皮脂への耐性とをいずれも向上できることを見出した。これにより、本発明を完成させるに至った。このような衝撃吸収層とすることにより、落下等の衝撃が加わった場合であっても、衝撃によるエネルギーが熱として又は変形により効果的に発散され、両面粘着シートの剥がれが抑制される。また、皮脂に曝された場合であっても、衝撃吸収層の緻密性が高いため脂分の浸入及び吸収が抑制され、両面粘着シートの剥がれが抑制される。 In the pressure-sensitive adhesive tape having a foam as a base material, the oil accumulates in the bubble portion of the foam by being exposed to sebum, and the fat oozes out into the pressure-sensitive adhesive layer. I found that it would lead to peeling. Therefore, it was considered to use a non-foamed material instead of the foam as the base material, but the non-foamed material was dissolved or swollen by contact with sebum, and the shape collapsed, and the adhesive tape could be peeled off.
In the shock absorbing sheet having a shock absorbing layer, which is preferably used as the base material of the double-sided pressure-sensitive adhesive sheet, the present inventors set the maximum value of the loss tangent tan δ at a specific frequency at 23 ° C. of the shock absorbing layer to a specific value or more. It was found that both the impact resistance and the resistance to sebum can be improved by adjusting the crystallinity to a specific value or more. As a result, the present invention has been completed. By using such an impact absorbing layer, even when an impact such as dropping is applied, the energy due to the impact is effectively dissipated as heat or due to deformation, and peeling of the double-sided pressure-sensitive adhesive sheet is suppressed. Moreover, even when exposed to sebum, the denseness of the shock absorbing layer is high, so that the penetration and absorption of fat are suppressed, and peeling of the double-sided pressure-sensitive adhesive sheet is suppressed.
上記衝撃吸収層は、23℃における周波数1.0×103~1.0×106.5Hzでの損失正接tanδの最大値が0.7以上、かつ、結晶化度が2%以上である。 The shock absorbing sheet of the present invention has a shock absorbing layer.
The shock absorbing layer has a maximum loss tangent tan δ of 0.7 or more at a frequency of 1.0 × 10 3 to 1.0 × 10 6.5 Hz at 23 ° C. and a crystallinity of 2% or more. is there.
上記損失正接tanδの最大値の上限は特に限定されないが、上記衝撃吸収層における粘性成分が多くなって上記損失正接tanδの最大値が大きくなりすぎると、上記衝撃吸収層が衝撃を吸収した際に塑性変形しやすくなるため、好ましい上限は3.0、より好ましい上限は2.7である。 When the maximum value of the loss tangent tan δ is 0.7 or more, the impact resistance of the shock absorbing layer is improved. For this reason, even when a shock such as a drop is applied when the shock-absorbing sheet of the present invention is used as a base material for a double-sided pressure-sensitive adhesive sheet, energy due to the shock is effectively dissipated as heat or due to deformation. Peeling of the pressure sensitive adhesive sheet is suppressed. The maximum value of the loss tangent tan δ may be 0.7 or more, but is preferably 0.8 or more, and more preferably 0.9 or more.
The upper limit of the maximum value of the loss tangent tan δ is not particularly limited, but when the viscous component in the shock absorbing layer increases and the maximum value of the loss tangent tan δ becomes too large, the shock absorbing layer absorbs the shock. A preferred upper limit is 3.0, and a more preferred upper limit is 2.7, because plastic deformation is likely.
ここで周波数1.0×103~1.0×106.5Hzとは、上記衝撃吸収層に対して、数十センチメートルから1メートル数十センチメートルの高さから物体を自由落下させたとき、上記衝撃吸収層が数マイクロメートルから数十マイクロメートル変位するときの周波数を想定した周波数である。即ち、携帯電子機器に落下等の衝撃が加わった場合を想定した周波数である。 The maximum value of the loss tangent tan δ at a frequency of 1.0 × 10 3 to 1.0 × 10 6.5 Hz at 23 ° C. is a dynamic viscoelasticity measuring device (for example, Rheogel-E4000 manufactured by UBM). It can be judged by measuring the elastic modulus of the shock absorbing layer using, and synthesizing a master curve. At this time, the “maximum value” of the loss tangent tan δ does not necessarily have to exist within the frequency range of 1.0 × 10 3 to 1.0 × 10 6.5 Hz. However, since the “maximum value” exists in the frequency range of 1.0 × 10 3 to 1.0 × 10 6.5 Hz, an impact was applied to the shock absorbing layer at a temperature higher or lower than 23 ° C. Even in this case, the shock absorbing layer can easily absorb the shock stably.
Here, the frequency of 1.0 × 10 3 to 1.0 × 10 6.5 Hz means that an object can be freely dropped from a height of several tens of centimeters to one tens of centimeters with respect to the shock absorbing layer. Then, the frequency assumes a frequency when the shock absorbing layer is displaced from several micrometers to several tens of micrometers. That is, the frequency is assumed when an impact such as dropping is applied to the portable electronic device.
上記結晶構造を有するオレフィン系エラストマーのうち、ランダム共重合体として、例えば、直鎖状低密度ポリエチレン(LLDPE)、高密度ポリエチレン(HDPE)等が挙げられる。また、ブロック共重合体として、例えば、オレフィン結晶-エチレン-ブチレン-オレフィン結晶(CEBC)ブロックポリマー、スチレン-エチレン-ブチレン-オレフィン結晶(SEBC)ブロックポリマー等が挙げられる。これらの結晶構造を有するオレフィン系エラストマーは単独で用いてもよいし、2種以上を併用してもよい。なかでも、直鎖部分が連続することで結晶構造がより密になることから、CEBCブロックポリマーが好ましい。
上記結晶構造を有するオレフィン系エラストマーは、架橋タイプであると柔軟性が発現しにくいため、非架橋タイプであることが好ましい。 The olefin elastomer having the above crystal structure may be a random copolymer or a block copolymer.
Among the olefin elastomers having the crystal structure, examples of the random copolymer include linear low density polyethylene (LLDPE) and high density polyethylene (HDPE). Examples of the block copolymer include olefin crystal-ethylene-butylene-olefin crystal (CEBC) block polymer, styrene-ethylene-butylene-olefin crystal (SEBC) block polymer, and the like. These olefinic elastomers having a crystal structure may be used alone or in combination of two or more. Of these, the CEBC block polymer is preferred because the crystal structure becomes denser due to the continuous linear portion.
The olefin-based elastomer having the crystal structure is preferably a non-crosslinked type because it is difficult to exhibit flexibility when it is a crosslinked type.
この場合、上記結晶構造を有するオレフィン系エラストマーと、上記他のエラストマーとの溶解パラメータ(SP値)の差が2以下であることが好ましい。上記SP値の差が2以下であることにより、上記結晶構造を有するオレフィン系エラストマーと上記他のエラストマーとの相溶性が高くなり、本発明の衝撃吸収シートを両面粘着シートの基材として用いた際に、小さい面積であっても、両面粘着シートが安定した性能を発揮することができる。上記SP値の差は1以下であることがより好ましい。
なお、溶解パラメータ(SP値)(単位:(cal/cm3)1/2)とは、樹脂又はエラストマー間の親和性を表す指標であり、例えば、下記に示すFedors式により算出することができる。 The olefin elastomer having the crystal structure may be used in combination with other elastomers.
In this case, the difference in solubility parameter (SP value) between the olefin elastomer having the crystal structure and the other elastomer is preferably 2 or less. When the difference in SP value is 2 or less, the compatibility between the olefin elastomer having the crystal structure and the other elastomer is increased, and the shock absorbing sheet of the present invention is used as a base material for a double-sided pressure-sensitive adhesive sheet. In particular, even if the area is small, the double-sided PSA sheet can exhibit stable performance. The difference in SP value is more preferably 1 or less.
The solubility parameter (SP value) (unit: (cal / cm 3 ) 1/2 ) is an index representing the affinity between the resin or the elastomer, and can be calculated by, for example, the Fedors equation shown below. .
上記スチレン系エラストマーとして、具体的には例えば、スチレン-ブタジエン-スチレン(SBS)ブロックコポリマー、スチレン-ブタジエン-ブチレン-スチレン(SBBS)ブロックコポリマー、スチレン-エチレン-ブチレン-スチレン(SEBS)ブロックコポリマー、水添スチレン-ブチレンゴム(HSBR)、スチレン-エチレン-プロピレン-スチレン(SEPS)ブロックコポリマー、スチレン-イソブチレン-スチレン(SIBS)ブロックコポリマー、スチレン-イソプレン-スチレン(SIS)ブロックコポリマー等が挙げられる。なかでも、分子構造の中に2重結合をもたず、熱及び光に比較的安定であることから、SEBS、SEPSがより好ましい。 The styrene-based elastomer is not particularly limited as long as it has rubber elasticity at room temperature. As the styrene-based elastomer, a styrene-based elastomer having a diblock or triblock structure of a polystyrene layer called a hard segment and a soft segment such as ethylene-butylene, ethylene-propylene, or ethylene-butadiene is more preferable.
Specific examples of the styrenic elastomer include styrene-butadiene-styrene (SBS) block copolymer, styrene-butadiene-butylene-styrene (SBBS) block copolymer, styrene-ethylene-butylene-styrene (SEBS) block copolymer, water Examples thereof include styrene-butylene rubber (HSBR), styrene-ethylene-propylene-styrene (SEPS) block copolymer, styrene-isobutylene-styrene (SIBS) block copolymer, and styrene-isoprene-styrene (SIS) block copolymer. Among these, SEBS and SEPS are more preferable because they do not have a double bond in the molecular structure and are relatively stable to heat and light.
なお、スチレン系エラストマー中のスチレン等の各ブロックの含有量は、1H-NMR(1H-核磁気共鳴)測定や13C-NMRによって測定することができる。 The styrene content of the styrenic elastomer is not particularly limited, but a preferred lower limit is 3% by weight and a preferred upper limit is 30% by weight. When the styrene content is 3% by weight or more, the heat resistance or cohesion of the shock absorbing layer is improved. When the styrene content is 30% by weight or less, the flexibility of the styrene-based elastomer is increased, the maximum value of the loss tangent tan δ is increased, and the impact resistance of the shock absorbing layer is improved. A more preferable lower limit of the styrene content is 4% by weight, and a more preferable upper limit is 25% by weight, a still more preferable lower limit is 5% by weight, and a still more preferable upper limit is 20% by weight.
The content of each block such as styrene in the styrene elastomer can be measured by 1 H-NMR (1H-nuclear magnetic resonance) measurement or 13 C-NMR.
特に、上記スチレン系エラストマーがSEBSやHSBRである場合はソフトセグメントにおけるエチレン骨格の含有量が上記範囲であることが好ましい。また、上記スチレン系エラストマーがSEBSやHSBRである場合はソフトセグメントにおけるエチレン骨格の含有量が3重量%以上であることが好ましく、4重量%以上であることがより好ましく、5重量%以上であることが更に好ましい。上記スチレン系エラストマーがSEBSやHSBRである場合に上記エチレン骨格の含有量が3重量%以上であると、上記衝撃吸収層が適度なガラス転移温度となるため、上記損失正接tanδの最大値を上記範囲に調整しやすくなる。また、SEBSのブチレン骨格は立体障害が大きく、結晶化を阻害し易い構造のため、tanδの値が高くなり衝撃吸収性を発揮し易くなる。そのため、上記スチレン系エラストマーがSEBSである場合のソフトセグメントにおけるブチレン骨格の含有量は特に限定されないが、45重量%以上であることが好ましい。上記ブチレン骨格の含有量を45重量%以上とすることにより、優れた耐衝撃性を発揮することができる。上記ブチレン骨格の含有量は60重量%以上であることがより好ましく、70重量%以上であることが更に好ましい。
SEPSは、エチレン骨格が3つ以上連続して連なることがないことから結晶化が起こりにくく、また、プロピレン骨格がかさ高いことから、tanδの値が高くなり、衝撃吸収性を発現しやすい。
SBBSがソフトセグメント中に有する1,4-ブタジエンの骨格も、エチレン骨格と同様に結晶化が進みやすく、柔軟性を損なうことがあり、その結果tanδの最大値が低下し耐衝撃性が低下することがある。そのためSBBSのソフトセグメントにおけるエチレンと1,4-ブタジエンの合計の含有量は、60重量%以下であることが好ましく、50重量%以下であることがより好ましく、40重量%以下であることが更に好ましい。
SIBS等に含まれるイソブチレン骨格は結晶化し難いため、tanδを高く制御することが可能であるが、tanδのピーク値の周波数が規定の範囲外になる可能性があるため、ソフトセグメント中にエチレン骨格等を導入し、tanδピーク位置を調整することがより好ましい。 The content of the ethylene skeleton in the soft segment of the styrene-based elastomer is not particularly limited, but a preferable upper limit in 100% by weight of the entire soft segment is 60% by weight. When the content of the ethylene skeleton is 60% by weight or less, the flexibility of the styrenic elastomer is increased, the maximum value of the loss tangent tan δ is increased, and the impact resistance of the shock absorbing layer is improved. A more preferable upper limit of the content of the ethylene skeleton is 50% by weight, and a more preferable upper limit is 40% by weight.
In particular, when the styrene elastomer is SEBS or HSBR, the content of the ethylene skeleton in the soft segment is preferably in the above range. Further, when the styrene elastomer is SEBS or HSBR, the content of the ethylene skeleton in the soft segment is preferably 3% by weight or more, more preferably 4% by weight or more, and more preferably 5% by weight or more. More preferably. When the styrene-based elastomer is SEBS or HSBR and the ethylene skeleton content is 3% by weight or more, the shock absorbing layer has an appropriate glass transition temperature, so the maximum value of the loss tangent tan δ is Easy to adjust to the range. In addition, since the butylene skeleton of SEBS has a large steric hindrance and a structure that easily inhibits crystallization, the value of tan δ is increased and it is easy to exhibit shock absorption. Therefore, the content of the butylene skeleton in the soft segment when the styrene-based elastomer is SEBS is not particularly limited, but is preferably 45% by weight or more. By setting the content of the butylene skeleton to 45% by weight or more, excellent impact resistance can be exhibited. The content of the butylene skeleton is more preferably 60% by weight or more, and further preferably 70% by weight or more.
SEPS is less likely to be crystallized because three or more ethylene skeletons are not continuously connected, and since the propylene skeleton is bulky, the value of tan δ is high, and shock absorption is likely to occur.
Similar to the ethylene skeleton, the 1,4-butadiene skeleton that SBBS has in the soft segment can be easily crystallized, and the flexibility may be impaired. As a result, the maximum value of tan δ is lowered and impact resistance is lowered. Sometimes. Therefore, the total content of ethylene and 1,4-butadiene in the SBBS soft segment is preferably 60% by weight or less, more preferably 50% by weight or less, and further preferably 40% by weight or less. preferable.
Since the isobutylene skeleton contained in SIBS or the like is difficult to crystallize, tan δ can be controlled to be high, but since the frequency of the peak value of tan δ may be outside the specified range, the ethylene skeleton is included in the soft segment. More preferably, the tan δ peak position is adjusted.
上記粘着付与樹脂は特に限定されず、例えば、テルペン系樹脂、ロジン系樹脂、石油系樹脂等が挙げられる。 The impact absorbing layer may contain a tackifier resin. By blending a tackifying resin into the impact absorbing layer, the maximum value of the loss tangent tan δ can be easily adjusted to the above range.
The tackifying resin is not particularly limited, and examples thereof include a terpene resin, a rosin resin, and a petroleum resin.
上記軟化剤は特に限定されず、例えば、石油系軟化剤(パラフィン系オイル)、液状ゴム系軟化剤、二塩基酸エステル、植物系軟化剤、油系軟化剤等が挙げられる。上記軟化剤は、上記衝撃吸収層を構成する樹脂との溶解パラメータ(SP値)の差が小さいことが好ましい。上記軟化剤のSP値は、9以下であることが好ましい。このような軟化剤を用いることで、上記衝撃吸収層の表面に軟化剤がブリードすることによる層間剥離を抑制しつつ、柔軟性を向上させることができる。上記石油系軟化剤(パラフィン系オイル)として、例えば、フッコールフレックス2050N(富士興産社製)、ダイアナプロセスオイルPW90(出光興産社製)等が挙げられる。上記液状ゴム系軟化剤としてポリブテンが挙げられる。上記ポリブテンは、数平均分子量が1000以上であることが好ましい。 The impact absorbing layer may contain a softening agent. When the impact absorbing layer contains a softening agent, flexibility is improved and impact resistance is improved. In addition, since the impact absorbing layer contains a softening agent, the adhesion between the double-sided pressure-sensitive adhesive sheet of the present invention and the adherend is improved when the shock-absorbing sheet of the present invention is used as a base material of the double-sided pressure-sensitive adhesive sheet. To do.
The softener is not particularly limited, and examples thereof include petroleum softeners (paraffinic oil), liquid rubber softeners, dibasic acid esters, plant softeners, oil softeners, and the like. The softening agent preferably has a small difference in solubility parameter (SP value) with the resin constituting the shock absorbing layer. The SP value of the softening agent is preferably 9 or less. By using such a softening agent, it is possible to improve flexibility while suppressing delamination caused by bleeding of the softening agent on the surface of the shock absorbing layer. Examples of the petroleum softener (paraffinic oil) include Fukkorflex 2050N (Fuji Kosan Co., Ltd.), Diana Process Oil PW90 (Idemitsu Kosan Co., Ltd.), and the like. An example of the liquid rubber softener is polybutene. The polybutene preferably has a number average molecular weight of 1000 or more.
上記酸化防止剤又は紫外線吸収剤は特に限定されず、例えば、フェノール系、アミン系、ベンズイミダゾール系等の酸化防止剤又は紫外線吸収剤が挙げられる。上記フェノール系酸化防止剤として、例えば、ノクラックNS-6(大内新興化学工業社製)等が挙げられる。上記紫外線吸収剤として、例えば、SEESORB 101(シプロ社製)等が挙げられる。 The impact absorbing layer may contain an antioxidant or an ultraviolet absorber because weather resistance is improved.
The antioxidant or ultraviolet absorber is not particularly limited, and examples thereof include phenol-based, amine-based, and benzimidazole-based antioxidants and ultraviolet absorbers. Examples of the phenolic antioxidant include NOCRACK NS-6 (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.). Examples of the ultraviolet absorber include SEESORB 101 (manufactured by Cypro Corporation).
上記着色剤は特に限定されず、携帯電子機器を構成する部品を機器本体に接着固定するために用いられる粘着シートに一般的に配合される顔料、染料等を用いることができる。上記着色剤として、例えば、ファーネスブラック、サーマルブラック、アセチレンブラック、チャンネルブラック、ランプブラック、ケッチェンブラック等のカーボンブラック等が挙げられる。また、酸化鉄、酸化チタン、酸化亜鉛、酸化マグネシウム、酸化コバルト、酸化銅、酸化クロム、アルミナ等の酸化物;硫酸カルシウム、硫酸バリウム、硫酸鉄、硫酸水銀等の硫酸塩;炭酸カルシウム、炭酸マグネシウム、ドロマイト等の炭酸塩等が挙げられる。また、鉄粉、銅粉、錫粉、鉛粉、アルミニウム粉等の金属粉;アゾ系顔料、フタロシアニン系顔料、ジオキサジン系顔料等の有機系顔料;黒鉛等が挙げられる。なかでも、カーボンブラックが好ましい。 The shock absorbing layer is preferably colored. By coloring the shock absorbing layer, the light of the liquid crystal display panel incorporated in the portable electronic device can be shielded by the shock absorbing layer.
The colorant is not particularly limited, and pigments, dyes, and the like that are generally blended in pressure-sensitive adhesive sheets used for bonding and fixing components constituting a portable electronic device to the device main body can be used. Examples of the colorant include carbon black such as furnace black, thermal black, acetylene black, channel black, lamp black, and ketjen black. In addition, oxides such as iron oxide, titanium oxide, zinc oxide, magnesium oxide, cobalt oxide, copper oxide, chromium oxide, and alumina; sulfates such as calcium sulfate, barium sulfate, iron sulfate, and mercury sulfate; calcium carbonate, magnesium carbonate And carbonates such as dolomite. Moreover, metal powders such as iron powder, copper powder, tin powder, lead powder and aluminum powder; organic pigments such as azo pigments, phthalocyanine pigments and dioxazine pigments; graphite and the like. Of these, carbon black is preferable.
なお、OD値は、ヘイズメーター(例えば、日本電色工業社製のNDH4000)により測定することができる。 The preferable lower limit of the OD value of the shock absorbing layer is 2, and the preferable upper limit is 7. When the OD value is 2 or more, the shock absorbing layer can sufficiently suppress light transmission both in the width direction and in the thickness direction. When the OD value is 7 or less, the flexibility of the shock absorbing layer is not impaired and the impact resistance can be maintained. The more preferable lower limit of the OD value is 4, and the more preferable upper limit is 6.
The OD value can be measured with a haze meter (for example, NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.).
上記微粒子は特に限定されず、例えば、シリカ、タルク、マイカ、アルミナ等からなるセラミック微粒子、銅、ニッケル、コバルト、金等からなる金属微粒子、ポリアミド樹脂、アクリル樹脂、エポキシ樹脂、エーテルスルホン樹脂、ポリアミドイミド樹脂等からなるプラスチック微粒子、シリカ又は樹脂ポリマーからなる中空微粒子等が挙げられる。
また、上記衝撃吸収層は、柔軟性を付与する等の目的で、発泡構造を有していてもよい。上記発泡構造の形成方法として、例えば、発泡剤による化学発泡、ガス混錬等による物理発泡、中空微粒子を混ぜる等の方法が挙げられる。 The impact absorbing layer may contain fine particles for the purpose of imparting heat resistance, rigidity, conductivity, etc., or weight reduction.
The fine particles are not particularly limited. For example, ceramic fine particles made of silica, talc, mica, alumina, etc., metal fine particles made of copper, nickel, cobalt, gold, etc., polyamide resin, acrylic resin, epoxy resin, ether sulfone resin, polyamide Examples thereof include plastic fine particles made of imide resin and the like, and hollow fine particles made of silica or a resin polymer.
The shock absorbing layer may have a foam structure for the purpose of imparting flexibility. Examples of the method for forming the foam structure include chemical foaming with a foaming agent, physical foaming by gas kneading, and the like, and mixing hollow fine particles.
また、本発明の衝撃吸収シートに占める上記衝撃吸収層の厚み割合は特に限定されないが、衝撃吸収シートが優れた耐衝撃性を有するためには、好ましい下限は40%、より好ましい下限は50%である。 Although the thickness of the said shock absorption layer is not specifically limited, A preferable minimum is 50 micrometers and a preferable upper limit is 400 micrometers. If the said thickness is 50 micrometers or more, the intensity | strength of the said shock absorption layer will become enough, and impact resistance will improve. If the said thickness is 400 micrometers or less, it can respond to the needs of thickness reduction of the recent adhesive sheet. A more preferable upper limit of the thickness is 300 μm.
Further, the thickness ratio of the shock absorbing layer in the shock absorbing sheet of the present invention is not particularly limited. However, in order for the shock absorbing sheet to have excellent impact resistance, the preferable lower limit is 40%, and the more preferable lower limit is 50%. It is.
上記外層を有することにより、上記衝撃吸収層への脂分の浸入及び吸収がより抑制され、衝撃吸収シートの皮脂への耐性が向上する。また、衝撃吸収シートの打ち抜き加工性及び取り扱い性も向上する。 The shock absorbing sheet of the present invention preferably further has an outer layer laminated and integrated on at least one surface of the shock absorbing layer. The outer layer may be formed only on one side of the shock absorbing layer or may be formed on both sides.
By having the outer layer, the penetration and absorption of fat into the shock absorbing layer are further suppressed, and the resistance of the shock absorbing sheet to sebum is improved. Moreover, the punching workability and handleability of the shock absorbing sheet are also improved.
上記引張弾性率の上限は特に限定されないが、高すぎると上記外層の柔軟性が低下し、上記衝撃吸収層との積層体の耐衝撃性が低下することがあるため、好ましい上限は2000MPa、より好ましい上限は1800MPaである。
なお、引張弾性率は、ASTM D638法に準拠して測定することができる。 The outer layer preferably has a tensile modulus of 200 MPa or more. If the said tensile elasticity modulus is 200 Mpa or more, the tolerance to sebum of an impact-absorbing sheet, punching workability, and handleability will improve more.
The upper limit of the tensile elastic modulus is not particularly limited, but if it is too high, the flexibility of the outer layer is lowered, and the impact resistance of the laminate with the shock absorbing layer may be lowered. Therefore, the preferred upper limit is 2000 MPa, more A preferable upper limit is 1800 MPa.
The tensile modulus can be measured according to the ASTM D638 method.
上記ポリオレフィンとしては、高密度ポリエチレン(HDPE)、低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE)、ポリプロピレン(PP)等が挙げられる。上記熱可塑性エラストマーとしては、ポリアミド(PA)、ポリブチレンテレフタレート(PBT)が挙げられる。 The resin which comprises the said outer layer is not specifically limited, For example, polyolefin, a thermoplastic elastomer, etc. are mentioned. Especially, by using polyolefin, the anchor property of the said shock absorption layer and the said outer layer becomes favorable, and can suppress the dispersion | variation in impact resistance.
Examples of the polyolefin include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and polypropylene (PP). Examples of the thermoplastic elastomer include polyamide (PA) and polybutylene terephthalate (PBT).
例えば、上記衝撃吸収層に導電性フィルムを積層することにより、衝撃吸収シートに導電性を付与することができる。また、上記衝撃吸収層にプライマーを塗布することにより、上記衝撃吸収層と後述する粘着剤層との密着性を上げたり、上記衝撃吸収層に様々な性能を付与したりすることができる。 The impact absorbing sheet of the present invention may further have other layers.
For example, electroconductivity can be provided to an impact-absorbing sheet by laminating a conductive film on the impact-absorbing layer. Further, by applying a primer to the shock absorbing layer, adhesion between the shock absorbing layer and a pressure-sensitive adhesive layer to be described later can be improved, or various performances can be imparted to the shock absorbing layer.
また、これらの用途における本発明の衝撃吸収シートの形状は特に限定されないが、長方形、額縁状、円形、楕円形、ドーナツ型等が挙げられる。 The use of the shock absorbing sheet of the present invention is not particularly limited, but it can be used as a base material for a pressure sensitive adhesive sheet for bonding and fixing components constituting a portable electronic device to the main body of a device or a pressure sensitive adhesive sheet for bonding and fixing a vehicle-mounted component Is preferred. The portable electronic device is not limited to a conventional rigid portable electronic device, and may be a portable electronic device that is exposed to more severe conditions such as a wearable terminal and a bendable (bending) terminal.
Moreover, the shape of the impact-absorbing sheet of the present invention in these uses is not particularly limited, and examples thereof include a rectangle, a frame shape, a circle, an ellipse, and a donut shape.
上記アクリル粘着剤は特に限定されないが、含フッ素(メタ)アクリレートに由来する構成単位を有する(メタ)アクリレート共重合体(以下、「含フッ素(メタ)アクリレート共重合体」ともいう)を含有することが好ましい。
なお、本明細書中において(メタ)アクリレートとは、アクリレート又はメタクリレートを意味する。 Although the said adhesive layer is not specifically limited, It is preferable to contain an acrylic adhesive.
The acrylic pressure-sensitive adhesive is not particularly limited, but contains a (meth) acrylate copolymer having a structural unit derived from fluorine-containing (meth) acrylate (hereinafter also referred to as “fluorine-containing (meth) acrylate copolymer”). It is preferable.
In the present specification, (meth) acrylate means acrylate or methacrylate.
上記含フッ素(メタ)アクリレート共重合体が上記架橋性官能基を有するモノマーに由来する構成単位を含有すると、架橋剤を併用したときに含フッ素(メタ)アクリレート共重合体鎖間が架橋される。その際、架橋度を調節することでゲル分率及び膨潤率を調節することができる。 The fluorine-containing (meth) acrylate copolymer preferably further contains a structural unit derived from a monomer having a crosslinkable functional group.
When the fluorine-containing (meth) acrylate copolymer contains a structural unit derived from the monomer having the crosslinkable functional group, the fluorine-containing (meth) acrylate copolymer chain is crosslinked when a crosslinking agent is used in combination. . At that time, the gel fraction and the swelling ratio can be adjusted by adjusting the degree of crosslinking.
カルボキシル基を有するモノマーとしては、例えば、(メタ)アクリル酸が挙げられる。
グリシジル基を有するモノマーとしては、例えば、グリシジル(メタ)アクリレートが挙げられる。
アミド基を有するモノマーとしては、例えば、ヒドロキシエチルアクリルアミド、イソプロピルアクリルアミド、ジメチルアミノプロピルアクリルアミド等が挙げられる。
ニトリル基を有するモノマーとしては、例えば、アクリロニトリル等が挙げられる。これらの架橋性官能基を有するモノマーは単独で用いてもよく、複数を併用してもよい。 Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, and a nitrile group. Especially, since adjustment of the gel fraction of the said adhesive layer is easy, a hydroxyl group or a carboxyl group is preferable. Examples of the monomer having a hydroxyl group include (meth) acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
As a monomer which has a carboxyl group, (meth) acrylic acid is mentioned, for example.
Examples of the monomer having a glycidyl group include glycidyl (meth) acrylate.
Examples of the monomer having an amide group include hydroxyethyl acrylamide, isopropyl acrylamide, dimethylaminopropyl acrylamide and the like.
Examples of the monomer having a nitrile group include acrylonitrile. These monomers having a crosslinkable functional group may be used alone or in combination.
なお、重量平均分子量(Mw)は、重合条件(例えば、重合開始剤の種類又は量、重合温度、モノマー濃度等)によって調整できる。重量平均分子量(Mw)とは、GPC(Gel Permeation Chromatography:ゲルパーミエーションクロマトグラフィ)による標準ポリスチレン換算の重量平均分子量である。 The fluorine-containing (meth) acrylate copolymer preferably has a lower limit of 500,000 and an upper limit of 2,000,000 for the weight average molecular weight (Mw). By the said weight average molecular weight being the said range, the adhesive force of the said adhesive layer improves and the impact resistance of a double-sided adhesive sheet improves. The minimum with said more preferable weight average molecular weight is 600,000, and a more preferable upper limit is 1,200,000.
The weight average molecular weight (Mw) can be adjusted by polymerization conditions (for example, the type or amount of polymerization initiator, polymerization temperature, monomer concentration, etc.). The weight average molecular weight (Mw) is a weight average molecular weight in terms of standard polystyrene by GPC (Gel Permeation Chromatography).
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、イソシアネート系架橋剤、エポキシ系架橋剤が好ましい。
上記架橋剤の配合量は、上記含フッ素(メタ)アクリレート共重合体100重量部に対して0.01~10重量部が好ましく、0.1~5重量部がより好ましい。 The acrylic pressure-sensitive adhesive preferably contains a crosslinking agent. When the said fluorine-containing (meth) acrylate copolymer has a structural unit derived from the monomer which has the said crosslinkable functional group, a crosslinked structure can be constructed | assembled with a crosslinking agent.
The said crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned. Of these, isocyanate crosslinking agents and epoxy crosslinking agents are preferred.
The amount of the crosslinking agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the fluorine-containing (meth) acrylate copolymer.
上記シランカップリング剤は特に限定されず、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルメチルジメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリメチルメトキシシラン、N-(2-アミノエチル)3-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)3-アミノプロピルメチルジメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルトリエトキシシラン、メルカプトブチルトリメトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン等が挙げられる。なかでも、γ-グリシドキシプロピルトリエトキシシランが好適である。 The acrylic pressure-sensitive adhesive may contain a silane coupling agent. When the acrylic pressure-sensitive adhesive contains a silane coupling agent, the adhesiveness of the pressure-sensitive adhesive layer to the adherend is improved, so that the resistance to sebum is improved.
The silane coupling agent is not particularly limited. For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethylmethoxysilane, N- (2-aminoethyl) 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylme Dimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, .gamma.-mercaptopropyl triethoxy silane, mercaptopropyl butyl trimethoxysilane, .gamma.-mercaptopropyl methyl dimethoxy silane, and the like. Of these, γ-glycidoxypropyltriethoxysilane is preferred.
まず、含フッ素(メタ)アクリレート共重合体、必要に応じて架橋剤等に溶剤を加えてアクリル粘着剤aの溶液を作製して、このアクリル粘着剤aの溶液を基材である衝撃吸収シートの表面に塗布し、溶液中の溶剤を完全に乾燥除去して粘着剤層aを形成する。次に、形成された粘着剤層aの上に離型フィルムをその離型処理面が粘着剤層aに対向した状態に重ね合わせる。
次いで、上記離型フィルムとは別の離型フィルムを用意し、この離型フィルムの離型処理面にアクリル粘着剤bの溶液を塗布し、溶液中の溶剤を完全に乾燥除去することにより、離型フィルムの表面に粘着剤層bが形成された積層フィルムを作製する。得られた積層フィルムの粘着剤層bを、衝撃吸収シートの裏面(粘着剤層aが形成されていない面)に対向させて重ね合わせ、積層体を作製する。そして、上記積層体をゴムローラ等によって加圧することによって、衝撃吸収シートの両面に粘着剤層を有し、かつ、粘着剤層の表面が離型フィルムで覆われた両面粘着シートを得ることができる。 As a manufacturing method of the double-sided adhesive sheet of this invention, the following methods are mentioned, for example.
First, a solution of an acrylic pressure-sensitive adhesive a is prepared by adding a solvent to a fluorine-containing (meth) acrylate copolymer and, if necessary, a crosslinking agent, etc., and the solution of the acrylic pressure-sensitive adhesive a is a base material for an impact absorbing sheet The adhesive layer a is formed by completely drying and removing the solvent in the solution. Next, the release film is superimposed on the formed pressure-sensitive adhesive layer a so that the release treatment surface faces the pressure-sensitive adhesive layer a.
Next, by preparing a release film different from the release film, applying a solution of acrylic adhesive b on the release treatment surface of the release film, and completely removing the solvent in the solution by drying, A laminated film having the pressure-sensitive adhesive layer b formed on the surface of the release film is produced. The pressure-sensitive adhesive layer b of the obtained laminated film is overlapped with the back surface of the shock absorbing sheet (the surface on which the pressure-sensitive adhesive layer a is not formed) to produce a laminate. Then, by pressing the laminate with a rubber roller or the like, a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on both sides of the impact-absorbing sheet and having the surface of the pressure-sensitive adhesive layer covered with a release film can be obtained. .
また、これらの用途における本発明の両面粘着シートの形状は特に限定されないが、長方形、額縁状、円形、楕円形、ドーナツ型等が挙げられる。 Although the use of the double-sided pressure-sensitive adhesive sheet of the present invention is not particularly limited, the use for bonding and fixing components constituting the portable electronic device to the device main body and the use for bonding and fixing vehicle-mounted components are preferable. Specifically, the double-sided pressure-sensitive adhesive sheet of the present invention can be used, for example, as a double-sided pressure-sensitive adhesive sheet that adheres and fixes a liquid crystal display panel of a portable electronic device to the device body. The portable electronic device is not limited to a conventional rigid portable electronic device, and may be a portable electronic device that is exposed to more severe conditions such as a wearable terminal and a bendable (bending) terminal.
Moreover, the shape of the double-sided pressure-sensitive adhesive sheet of the present invention in these applications is not particularly limited, and examples thereof include a rectangle, a frame shape, a circle, an ellipse, and a donut shape.
(1)衝撃吸収シートの製造
衝撃吸収層を構成する材料として、オレフィン結晶-エチレン-ブチレン-オレフィン結晶(CEBC)ブロックポリマー(JSR社製のダイナロン6200)100重量部と、カーボンブラック3重量部とを用いた。外層を構成する材料として、低密度ポリエチレン(LDPE)(表1中、PE)を用いた。
衝撃吸収層を構成する材料と外層を構成する材料とを200℃で溶融し、これらの溶融樹脂を押出しながら多層ダイ内で積層させた(共押出温度200℃)。その後、冷却することで、厚み60μmの非発泡の衝撃吸収層の両側にそれぞれ厚み10μmの外層が積層された衝撃吸収シートを得た。 Example 1
(1) Production of Shock Absorbing Sheet As materials constituting the shock absorbing layer, 100 parts by weight of olefin crystal-ethylene-butylene-olefin crystal (CEBC) block polymer (Dynalon 6200 manufactured by JSR), 3 parts by weight of carbon black, Was used. As a material constituting the outer layer, low density polyethylene (LDPE) (PE in Table 1) was used.
The material constituting the shock absorbing layer and the material constituting the outer layer were melted at 200 ° C., and these molten resins were laminated in a multilayer die while being extruded (coextrusion temperature 200 ° C.). Thereafter, by cooling, an impact absorbing sheet was obtained in which an outer layer having a thickness of 10 μm was laminated on both sides of a non-foamed impact absorbing layer having a thickness of 60 μm.
また、衝撃吸収層を30mm×30mmにカットし、X線回折装置(リガク社製のSmartLab)を使用して衝撃吸収層にX線を照射し、得られた回折情報(回折プロファイル)において、非晶部分に由来する散乱領域と結晶部分に由来する散乱領域とを分け、全散乱積分強度に対する結晶散乱積分強度の比として結晶化度を算出した。
また、ヘイズメーター(日本電色工業社製のNDH4000)により透過率を測定し、衝撃吸収層のOD値を算出した。
また、衝撃吸収層及び外層を構成するポリマーの構成単位及びFedors式をもとに、衝撃吸収層及び外層のSP値を算出した。
また、ASTM D638法に準拠して外層及び衝撃吸収シートの引張弾性率を算出した。 The shock absorbing layer was cut into a width of 5 mm × 30 mm, and the long side of 30 mm was chucked with a dynamic viscoelasticity measuring apparatus (Rheogel-E4000 manufactured by UBM) with a chuck interval of 15 mm. By measuring the tensile viscoelasticity in the range of −60 ° C. to 100 ° C. at a rate of temperature increase of 5 ° C./min and synthesizing a master curve at a reference temperature of 23 ° C., a frequency at 23 ° C. of 1.0 × 10 3 The maximum value of the loss tangent tan δ at 1.0 × 10 6.5 Hz was calculated. Further, the frequency at which the loss tangent tan δ takes the maximum value was confirmed.
Further, the shock absorbing layer was cut into 30 mm × 30 mm, and the shock absorbing layer was irradiated with X-rays using an X-ray diffractometer (SmartLab manufactured by Rigaku Corporation). In the obtained diffraction information (diffraction profile), The scattering region derived from the crystal portion and the scattering region derived from the crystal portion were separated, and the crystallinity was calculated as the ratio of the crystal scattering integrated intensity to the total scattering integrated intensity.
Further, the transmittance was measured with a haze meter (NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.), and the OD value of the shock absorbing layer was calculated.
The SP values of the shock absorbing layer and the outer layer were calculated based on the structural units of the polymers constituting the shock absorbing layer and the outer layer and the Fedors equation.
Moreover, the tensile elastic modulus of the outer layer and the impact absorbing sheet was calculated based on the ASTM D638 method.
反応容器内に、重合溶媒として酢酸エチルを加え、窒素でバブリングした後、窒素を流入しながら反応容器を加熱して還流を開始した。続いて、重合開始剤としてアゾビスイソブチロニトリル0.1重量部を酢酸エチルで10倍希釈した重合開始剤溶液を反応容器内に投入し、ブチルアクリレート63.5重量部、2,2,2-トリフルオロエチルアクリレート33.5重量部、アクリル酸3重量部を2時間かけて滴下添加した。滴下終了後、重合開始剤としてアゾビスイソブチロニトリル0.1重量部を酢酸エチルで10倍希釈した重合開始剤溶液を反応容器内に再度投入し、4時間重合反応を行い、(メタ)アクリレート共重合体含有溶液を得た。
得られた(メタ)アクリレート共重合体含有溶液に、架橋剤としてテトラッドC(三菱ガス化学社製)を(メタ)アクリレート共重合体100重量部に対して1重量部加え、粘着剤Aを得た。 (2) Preparation of pressure-sensitive adhesive A Ethyl acetate was added as a polymerization solvent in the reaction vessel, and after bubbling with nitrogen, the reaction vessel was heated while flowing nitrogen and refluxing was started. Subsequently, a polymerization initiator solution in which 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was diluted 10 times with ethyl acetate was charged into the reaction vessel, and 63.5 parts by weight of butyl acrylate, 2, 2, 33.5 parts by weight of 2-trifluoroethyl acrylate and 3 parts by weight of acrylic acid were added dropwise over 2 hours. After completion of the dropwise addition, a polymerization initiator solution obtained by diluting 0.1 parts by weight of azobisisobutyronitrile 10 times with ethyl acetate as a polymerization initiator was charged again into the reaction vessel, and a polymerization reaction was performed for 4 hours. An acrylate copolymer-containing solution was obtained.
To the obtained (meth) acrylate copolymer-containing solution, 1 part by weight of Tetrad C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a cross-linking agent is added to 100 parts by weight of the (meth) acrylate copolymer to obtain an adhesive A. It was.
シリコン離型処理が施された厚み75μmの離型PETフィルムに粘着剤Aをアプリケーターを用いて塗布し110℃で3分間乾燥し、厚み35μmの粘着剤層を形成した。この粘着剤層を上記で得られた衝撃吸収シートにシリコンローラーを用いて貼り合わせ、片面粘着シートを得た。なお、上記衝撃吸収シートには、予めコロナ処理装置(春日電機社製の「CT-0212」)を用いて270W、18m/minの条件で両面にコロナ処理を施した。
同様の要領で、衝撃吸収シートの反対の表面の離型PETフィルムを剥がし、上記と同じ粘着剤層を貼り合わせた。その後、40℃で48時間養生を行った。これにより、両面を離型PETフィルムで覆われた両面粘着シートを得た。 (3) Manufacture of double-sided pressure-sensitive adhesive sheet Adhesive A was applied to a 75 μm-thick release PET film that had been subjected to silicon release treatment using an applicator and dried at 110 ° C. for 3 minutes to form a 35 μm-thick pressure-sensitive adhesive layer did. This pressure-sensitive adhesive layer was bonded to the impact-absorbing sheet obtained above using a silicon roller to obtain a single-sided pressure-sensitive adhesive sheet. The shock absorbing sheet was previously subjected to corona treatment on both sides under the conditions of 270 W and 18 m / min using a corona treatment device (“CT-0212” manufactured by Kasuga Denki Co., Ltd.).
In the same manner, the release PET film on the surface opposite to the impact-absorbing sheet was peeled off, and the same pressure-sensitive adhesive layer as above was bonded. Thereafter, curing was performed at 40 ° C. for 48 hours. This obtained the double-sided adhesive sheet which both surfaces were covered with the mold release PET film.
衝撃吸収層にCEBCブロックポリマーのみの代わりにCEBCブロックポリマーと、スチレン-エチレン-プロピレン-スチレン(SEPS)ブロックコポリマー(クラレ社製のセプトン2063)とを用いた(CEBC:SEPS比率=8:2)こと以外は実施例1と同様にして、両面粘着シートを得た。 (Example 2)
Instead of only the CEBC block polymer, a CEBC block polymer and a styrene-ethylene-propylene-styrene (SEPS) block copolymer (Kuraray Septon 2063) were used for the shock absorbing layer (CEBC: SEPS ratio = 8: 2). Except for this, a double-sided PSA sheet was obtained in the same manner as Example 1.
CEBC:SEPS比率=6:4としたこと以外は実施例2と同様にして、両面粘着シートを得た。 (Example 3)
A double-sided PSA sheet was obtained in the same manner as in Example 2 except that the CEBC: SEPS ratio was 6: 4.
CEBC:SEPS比率=4:6としたこと以外は実施例2と同様にして、両面粘着シートを得た。 Example 4
A double-sided PSA sheet was obtained in the same manner as in Example 2 except that the CEBC: SEPS ratio was 4: 6.
外層にポリプロピレン(PP)を用いたこと以外は実施例1と同様にして、両面粘着シートを得た。 (Example 5)
A double-sided PSA sheet was obtained in the same manner as in Example 1 except that polypropylene (PP) was used for the outer layer.
カーボンブラックの配合量をブロックポリマー100重量部に対して1重量部としてOD値を2.5に調整したこと以外は実施例1と同様にして、両面粘着シートを得た。 (Example 6)
A double-sided PSA sheet was obtained in the same manner as in Example 1 except that the blending amount of carbon black was 1 part by weight with respect to 100 parts by weight of the block polymer and the OD value was adjusted to 2.5.
カーボンブラックの配合量をブロックポリマー100重量部に対して6重量部としてOD値を6.6に調整したこと以外は実施例1と同様にして、両面粘着シートを得た。 (Example 7)
A double-sided PSA sheet was obtained in the same manner as in Example 1 except that the blending amount of carbon black was 6 parts by weight with respect to 100 parts by weight of the block polymer and the OD value was adjusted to 6.6.
粘着剤の調製において、滴下添加したモノマーをブチルアクリレート23.5重量部、エチルアクリレート23.5重量部、2,2,2-トリフルオロエチルアクリレート50重量部、アクリル酸3重量部に変更して粘着剤Bを得たこと以外は実施例1と同様にして、両面粘着シートを得た。 (Example 8)
In the preparation of the pressure-sensitive adhesive, the monomer added dropwise was changed to 23.5 parts by weight of butyl acrylate, 23.5 parts by weight of ethyl acrylate, 50 parts by weight of 2,2,2-trifluoroethyl acrylate, and 3 parts by weight of acrylic acid. A double-sided PSA sheet was obtained in the same manner as Example 1 except that the PSA B was obtained.
粘着剤Aの代わりに粘着剤Bを用いたこと以外は実施例2と同様にして、両面粘着シートを得た。 Example 9
A double-sided PSA sheet was obtained in the same manner as in Example 2 except that PSA B was used instead of PSA A.
衝撃吸収層を構成する材料のみを用いて単層の溶融押出を行い、外層を形成しなかったこと以外は実施例1と同様にして、両面粘着シートを得た。 (Example 10)
A double-sided PSA sheet was obtained in the same manner as in Example 1 except that a single layer was melt-extruded using only the material constituting the shock absorbing layer and no outer layer was formed.
衝撃吸収層に軟化剤(ポリブテン、数平均分子量1350)を添加(CEBC30重量部に対して70重量部)したこと以外は実施例1と同様にして、両面粘着シートを得た。 (Example 11)
A double-sided PSA sheet was obtained in the same manner as in Example 1 except that a softening agent (polybutene, number average molecular weight 1350) was added to the shock absorbing layer (70 parts by weight with respect to 30 parts by weight of CEBC).
軟化剤の添加量を変更(CEBC50重量部に対して50重量部)したこと以外は実施例11と同様にして、両面粘着シートを得た。 (Example 12)
A double-sided PSA sheet was obtained in the same manner as in Example 11 except that the amount of the softening agent was changed (50 parts by weight with respect to 50 parts by weight of CEBC).
軟化剤を石油系軟化剤(パラフィン系オイル)(ダイアナプロセスオイルPW90、出光興産社製)に変更したこと以外は実施例12と同様にして、両面粘着シートを得た。 (Example 13)
A double-sided PSA sheet was obtained in the same manner as in Example 12 except that the softener was changed to a petroleum softener (paraffinic oil) (Diana Process Oil PW90, manufactured by Idemitsu Kosan Co., Ltd.).
衝撃吸収層にCEBCブロックポリマーの代わりにスチレン-エチレン-プロピレン-スチレン(SEPS)ブロックコポリマーを用いた(CEBC:SEPS比率=0:10)こと以外は実施例1と同様にして、両面粘着シートを得た。 (Comparative Example 1)
A double-sided PSA sheet was prepared in the same manner as in Example 1 except that a styrene-ethylene-propylene-styrene (SEPS) block copolymer was used instead of the CEBC block polymer (CEBC: SEPS ratio = 0: 10) for the shock absorbing layer. Obtained.
CEBC:SEPS比率=2:8としたこと以外は実施例2と同様にして、両面粘着シートを得た。 (Comparative Example 2)
A double-sided PSA sheet was obtained in the same manner as in Example 2 except that the CEBC: SEPS ratio was 2: 8.
衝撃吸収シートとしてPET(ポリエチレンテレフタレート)フィルム(東洋紡社製のE5100、厚み75μm)を用いたこと以外は実施例1と同様にして、両面粘着シートを得た。 (Comparative Example 3)
A double-sided PSA sheet was obtained in the same manner as in Example 1 except that a PET (polyethylene terephthalate) film (E5100 manufactured by Toyobo Co., Ltd., thickness 75 μm) was used as the impact absorbing sheet.
実施例、比較例で得られた両面粘着シートについて下記の評価を行った。結果を表1に示した。 <Evaluation>
The following evaluation was performed about the double-sided adhesive sheet obtained by the Example and the comparative example. The results are shown in Table 1.
<試験装置の作製>
図1に、実施例、比較例で得られた両面粘着シートの落下衝撃試験を示す模式図を示す。得られた両面粘着シートを外径が幅46mm、長さ61mm、内径が幅44mm、長さ59mmに打ち抜き、幅1mmの枠状の試験片を作製した。次いで、図1(a)に示すように、中央部分に幅38mm、長さ50mmの四角い穴のあいた厚さ2mmのポリカーボネート板43に対して離型紙を剥がした試験片41を四角い穴がほぼ中央に位置するように貼り付けた。その後、試験片41の上面から幅55mm、長さ65mm、厚さ1mmのポリカーボネート板42を試験片41がほぼ中央に位置するように貼り付け、試験装置を組み立てた。
その後、試験装置の上面に位置するポリカーボネート板側から5kgfの圧力を10秒間加えて上下に位置するポリカーボネート板と試験片とを圧着し、常温で24時間放置した。 (1) Drop impact test <Production of test equipment>
In FIG. 1, the schematic diagram which shows the drop impact test of the double-sided adhesive sheet obtained by the Example and the comparative example is shown. The obtained double-sided PSA sheet was punched into an outer diameter of 46 mm, a length of 61 mm, an inner diameter of 44 mm, and a length of 59 mm to produce a frame-shaped test piece having a width of 1 mm. Next, as shown in FIG. 1 (a), the
Thereafter, a pressure of 5 kgf was applied for 10 seconds from the side of the polycarbonate plate positioned on the upper surface of the test apparatus, and the polycarbonate plate positioned on the upper and lower sides and the test piece were pressed and left at room temperature for 24 hours.
図1(b)に示すように、作製した試験装置を裏返して支持台に固定し、四角い穴を通過する大きさの300gの重さの鉄球44を四角い穴を通過するように落とした。鉄球を落とす高さを徐々に高くしていき、鉄球の落下により加わった衝撃により試験片とポリカーボネート板が剥がれた時の鉄球を落した高さを計測した。
結果が70cm以上であった場合の判定を◎、50cm以上70cm未満であった場合の判定を○、50cm未満であった場合の判定を×とした。 <Drop impact resistance judgment>
As shown in FIG. 1 (b), the produced test apparatus was turned over and fixed to the support base, and an
The determination when the result was 70 cm or more was ◎, the determination when the result was 50 cm or more and less than 70 cm was ◯, and the determination when the result was less than 50 cm was ×.
実施例、比較例で得られた、外層を積層する前の衝撃吸収層について、幅20mm、長さ40mmの平面長方形状に裁断して試験片を作製し、重量を測定した。試験片をオレイン酸中に40℃、湿度90%の条件下にて24時間浸漬した後、試験片をオレイン酸から取り出し、エタノールで表面を洗浄後、70℃にて3時間乾燥させた。乾燥後の試験片の重量を測定し、下記式(1)を用いて衝撃吸収層のオレイン酸膨潤率を算出した。
膨潤率(重量%)=100×W5/W4 (1)
(W4:オレイン酸浸漬前の試験片の重量、W5:オレイン酸浸漬、乾燥後の試験片の重量) (2) Evaluation of sebum resistance (measurement of swelling rate of oleic acid)
About the impact-absorbing layer before laminating | stacking an outer layer obtained by the Example and the comparative example, it cut | judged in the planar rectangular shape of width 20mm and length 40mm, produced the test piece, and measured the weight. The test piece was immersed in oleic acid for 24 hours under conditions of 40 ° C. and 90% humidity, and then the test piece was taken out of oleic acid, washed with ethanol and then dried at 70 ° C. for 3 hours. The weight of the test piece after drying was measured, and the oleic acid swelling rate of the shock absorbing layer was calculated using the following formula (1).
Swelling ratio (% by weight) = 100 × W 5 / W 4 (1)
(W 4 : Weight of test piece before oleic acid immersion, W 5 : Weight of test piece after oleic acid immersion and drying)
実施例、比較例で得られた両面粘着シートを、切断加工機のカッターを上下に移動させることにより離型紙ごと厚み方向に切断し、額縁状に打ち抜いた。離型紙からの粘着剤層の浮き及びヨレの有無を目視にて確認した。
離型紙からの粘着剤層の浮きもヨレもなかった場合の判定を○、浮き又はヨレがあるが額縁状の打ち抜き形状を維持していた場合の判定を△、浮き又はヨレにより額縁状の打ち抜き形状を維持できなかった場合の判定を×とした。 (3) Evaluation of workability (punching evaluation)
The double-sided PSA sheets obtained in the examples and comparative examples were cut in the thickness direction together with the release paper by moving the cutter of the cutting machine up and down and punched into a frame shape. The presence or absence of lifting of the pressure-sensitive adhesive layer from the release paper and the twisting were visually confirmed.
Judgment when there is no lifting or twisting of the pressure-sensitive adhesive layer from the release paper ○, judgment when there is floating or twisting but maintaining the frame-like punching shape △, punching frame-like by lifting or twisting The case where the shape could not be maintained was evaluated as x.
実施例、比較例で得られた両面粘着シートの一方の面を厚さ2mmのガラス板に貼り付けた。このとき、両面粘着シートとガラス板が完全(接着面積が100%)に密着するように貼り付けた。次いで、厚さ3mmのアクリル板を準備し、10kgのローラーを1往復させて圧着することで、両面粘着シートの他方の面をアクリル板に貼り付けた。この試験片をアクリル板面側からデジタルカメラで撮影し(1920×1080ピクセル、4倍)、得られた画像を白黒2値化した(しきい値は最大濃度の1/2とした)。両面粘着シート全体の面積に対する黒部分の面積を、接着面積割合として算出した。 (4) Adhesion evaluation (adhesion area evaluation)
One surface of the double-sided PSA sheet obtained in the examples and comparative examples was attached to a glass plate having a thickness of 2 mm. At this time, the double-sided pressure-sensitive adhesive sheet and the glass plate were pasted so as to be in close contact with each other (the adhesion area was 100%). Next, an acrylic plate having a thickness of 3 mm was prepared, and the other surface of the double-sided pressure-sensitive adhesive sheet was attached to the acrylic plate by reciprocating a 10 kg roller once. This test piece was photographed with a digital camera from the acrylic plate surface side (1920 × 1080 pixels, 4 times), and the obtained image was binarized in black and white (the threshold value was set to 1/2 of the maximum density). The area of the black part with respect to the area of the whole double-sided pressure-sensitive adhesive sheet was calculated as a bonding area ratio.
42 ポリカーボネート板(厚さ1mm)
43 ポリカーボネート板(厚さ2mm)
44 鉄球(300g) 41 Test piece (frame shape)
42 Polycarbonate plate (1mm thickness)
43 Polycarbonate plate (2mm thick)
44 Iron ball (300 g)
Claims (8)
- 衝撃吸収層を有する衝撃吸収シートであって、
前記衝撃吸収層は、23℃における周波数1.0×103~1.0×106.5Hzでの損失正接tanδの最大値が0.7以上、かつ、結晶化度が2%以上である
ことを特徴とする衝撃吸収シート。 A shock absorbing sheet having a shock absorbing layer,
The shock absorbing layer has a maximum loss tangent tan δ of 0.7 or more and a crystallinity of 2% or more at a frequency of 1.0 × 10 3 to 1.0 × 10 6.5 Hz at 23 ° C. A shock absorbing sheet characterized by being. - 衝撃吸収層は、結晶構造を有するオレフィン系エラストマーを含有することを特徴とする請求項1記載の衝撃吸収シート。 The impact-absorbing sheet according to claim 1, wherein the impact-absorbing layer contains an olefin-based elastomer having a crystal structure.
- 衝撃吸収層は、OD値が7以下であることを特徴とする請求項1又は2記載の衝撃吸収シート。 The shock absorbing sheet according to claim 1 or 2, wherein the shock absorbing layer has an OD value of 7 or less.
- 更に、衝撃吸収層の少なくとも一方の面に積層一体化された外層を有し、前記外層は、引張弾性率が200MPa以上であることを特徴とする請求項1、2又は3記載の衝撃吸収シート。 4. The shock absorbing sheet according to claim 1, further comprising an outer layer laminated and integrated on at least one surface of the shock absorbing layer, wherein the outer layer has a tensile elastic modulus of 200 MPa or more. .
- 外層は、衝撃吸収層との溶解パラメータ(SP値)の差が2以下であることを特徴とする請求項4記載の衝撃吸収シート。 The impact absorbing sheet according to claim 4, wherein the outer layer has a difference in solubility parameter (SP value) of 2 or less from the impact absorbing layer.
- 請求項1、2、3、4又は5記載の衝撃吸収シートと、前記衝撃吸収シートの両面に積層一体化された粘着剤層とを有することを特徴とする両面粘着シート。 6. A double-sided pressure-sensitive adhesive sheet comprising the impact-absorbing sheet according to claim 1, and a pressure-sensitive adhesive layer laminated and integrated on both surfaces of the shock-absorbing sheet.
- 衝撃吸収層は、25%圧縮強度が930kPa以下であることを特徴とする請求項6記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to claim 6, wherein the impact absorbing layer has a 25% compressive strength of 930 kPa or less.
- 携帯電子機器を構成する部品を機器本体に接着固定するために用いられることを特徴とする請求項6又は7記載の両面粘着シート。
The double-sided pressure-sensitive adhesive sheet according to claim 6 or 7, wherein the double-sided pressure-sensitive adhesive sheet is used for adhering and fixing a part constituting the portable electronic device to the device main body.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201880016949.7A CN110418716A (en) | 2017-05-02 | 2018-04-27 | Impact-absorbing sheet and double-sided adhesive sheet |
KR1020197014763A KR20190141645A (en) | 2017-05-02 | 2018-04-27 | Shock Absorbing Sheet & Double Sided Adhesive Sheet |
JP2018525636A JPWO2018203537A1 (en) | 2017-05-02 | 2018-04-27 | Shock absorbing sheet and double-sided adhesive sheet |
US16/608,461 US20210107265A1 (en) | 2017-05-02 | 2018-04-27 | Impact absorption sheet and double-sided pressure-sensitive adhesive sheet |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2017091753 | 2017-05-02 | ||
JP2017-091753 | 2017-05-02 |
Publications (1)
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WO2018203537A1 true WO2018203537A1 (en) | 2018-11-08 |
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ID=64016607
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2018/017272 WO2018203537A1 (en) | 2017-05-02 | 2018-04-27 | Impact absorption sheet and double-sided pressure-sensitive adhesive sheet |
Country Status (6)
Country | Link |
---|---|
US (1) | US20210107265A1 (en) |
JP (1) | JPWO2018203537A1 (en) |
KR (1) | KR20190141645A (en) |
CN (1) | CN110418716A (en) |
TW (1) | TW201900741A (en) |
WO (1) | WO2018203537A1 (en) |
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WO2020129332A1 (en) * | 2018-12-17 | 2020-06-25 | 日東電工株式会社 | Image display panel with bezel, and image display device |
JP2020098320A (en) * | 2018-12-17 | 2020-06-25 | 日東電工株式会社 | Image display panel with bezel, image display device, and optical film with adhesive layer |
JP2020111738A (en) * | 2019-01-09 | 2020-07-27 | 積水化学工業株式会社 | Pressure sensitive adhesive tape |
WO2024117215A1 (en) * | 2022-12-02 | 2024-06-06 | リンテック株式会社 | Pressure-sensitive adhesive, pressure-sensitive adhesive sheet, laminated member, and display |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20220007750A (en) * | 2020-07-09 | 2022-01-19 | 삼성디스플레이 주식회사 | Display device |
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Also Published As
Publication number | Publication date |
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KR20190141645A (en) | 2019-12-24 |
US20210107265A1 (en) | 2021-04-15 |
CN110418716A (en) | 2019-11-05 |
TW201900741A (en) | 2019-01-01 |
JPWO2018203537A1 (en) | 2020-03-12 |
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